Ethylene alpha-olefin polymer substituted amine dispersant additives

ABSTRACT

The present invention is directed to an oil-soluble lubricating oil additive comprising at least one terminally unsaturated ethylene alpha-olefin polymer of 300 to 20,000 number average molecular weight terminally substituted with amine compounds, which are also useful additives to oleaginous compositions, e.g., as fuel and lubricating oil dispersants.

FIELD OF THE INVENTION

This invention relates to improved oil soluble dispersant additivesuseful in oleaginous compositions, including fuels and lubricating oilcompositions, and to concentrates containing said additives.

BACKGROUND OF THE INVENTION

Ashless nitrogen and ester containing lubricating oil dispersants havebeen widely used by the industry. Typically, these dispersants areprepared from a long chain hydrocarbon polymer by reacting the polymerwith maleic anhydride to form the corresponding polymer which issubstituted with succinic anhydride groups. Polyisobutylene has beenwidely used as the polymer of choice, chiefly because it is readilyavailable by cationic polymerization from butene streams (e.g., usingAlCl₃ catalysts). Such polyisobutylenes generally contain residualunsaturation in amounts of about one ethylenic double bond per polymerchain, positioned along the chain.

The polyisobutylene polymers (PIB) employed in most conventionaldispersants are based on a hydrocarbon chain of a number averagemolecular weight (M_(n)) of from about 900 to about 2500. PIB having aM_(n) of less than about 300 gives rather poor performance results whenemployed in dispersants because the molecular weight is insufficient tokeep the dispersant molecule fully solubilized in lubricating oils. Onthe other hand, high molecular weight PIB (M_(n) >3000) becomes soviscous that conventional industrial practices are incapable of handlingthis product in many operations. This problem becomes much more severeas the PIB molecular weight increases to 5000 or 10,000.

Increased amounts of terminal ethylenic unsaturation in polyisobutylene(so-called "reactive polyisobutylene") has been achieved by BF₃catalyzed polymerization of isobutylene. Exemplary of referencesdisclosing these polymers is U.S. Pat. No. 4,152,499. However, suchreactive polyisobutylene materials can still contain substantial amountsof unsaturation elsewhere along the chain. Further, it is difficult toproduce such reactive polyisobutylene polymers at molecular weights ofgreater than about 2,000, and, even so, the reactive polyisobutylenesthemselves still suffer the above-noted viscosity increase disadvantagesas molecular weights are increased.

Other polymers, such as ethylene-propylene co-polymers and terpolymerscontaining non-conjugated dienes, have been disclosed as suitablepolymers for the preparation of ashless nitrogen and ester dispersants.

U.S. Pat. No. 4,234,435, for example, discloses dispersants preparedfrom polyalkenes, M_(n) of 1,300 to about 5,000. The polyalkene cancomprise homopolymers or interpolymers of C₂ to C₁₆ terminal olefins, ofwhich ethylene-propylene copolymers are said to be examples, withspecific reference to a copolymer of 80% ethylene and 20% propylene.

However, ethylene-alpha-olefin copolymers of the above molecular weightscould be produced using Ziegler-Natta catalysts only in combination withH₂ as molecular weight control in order to terminate the growingcopolymer chains within this molecular weight range. Without use of H₂or other conventional, so-called "chain stoppers", the copolymersproduced with Ziegler-Natta catalysts would tend to have molecularweights greatly in excess of the above range. (Such higher copolymers,for example, are widely employed in ungrafted form as viscosity indeximprovers, and when grafted with nitrogen-containing groups, asdescribed below, are conventionally employed as dispersant-viscosityindex improver polymers.) The use of H₂ as a chain stopper has thedisadvantage of causing the saturation of the olefinic double bondcontent of the copolymer. Thus, while lower molecular weight copolymerswere theoretically possible to prepare, their low unsaturation content(and the accompanying low graft copolymer yields) would have made theirfurther functionalization by a thermal "ene" reaction, e.g., withdicarboxylic acid moieties in preparing dispersants, highlyunattractive.

U.S. Pat. No. 4,668,834 to Uniroyal Chemical discloses preparation (viacertain metallocene and a lumoxane catalyst systems) and composition ofethylene-alpha olefin copolymers and terpolymers having vinylidene-typeterminal unsaturation, which are disclosed to be useful as intermediatesin epoxy-grafted encapsulation compositions.

U.S. Pat. No. 4,704,491 to Mitsui Petrochemical relates to liquidethylene alpha-olefin random copolymers, useful when hydrogenated assynthetic lubricant oil, characterized inter alia by having 10-85 mol.%ethylene units, 15-90 mol.% alpha-olefin units, M_(n) of from 300 to10,000 and M_(w) /M_(n) of not more than 2.5. The patent also indicatesthat the liquid copolymer can be easily modified since it has a doublebond capable of reacting with maleic anhydride, etc., at the molecularchain ends.

Japanese Published Patent Application 87-129,303A of MitsuiPetrochemical relates to narrow molecular weight distribution (M_(n)/M_(n) <2.5) ethylene alpha-olefin copolymers containing 85-99 mol%ethylene, which are disclosed to be used for dispersing agents,modifiers or materials to produce toners. The copolymers havingcrystallinity of from 5-85%) are prepared in the presence of a catalystsystem comprising Zr compounds having at least one cycloalkadienyl groupand alumoxane.

European Patent 128,046 discloses (co)polyolefin reactor blends ofpolyethylene and ethylene higher alpha-olefin copolymers prepared byemploying described dual-metallocene/alumoxane catalyst systems.

European Patent Publication 129,368 discloses metallocene/alumoxanecatalysts useful for the preparation of ethylene homopolymer andethylene higher alpha-olefin copolymers.

European Patent Application Publication 257,696 Al relates to a processfor dimerizing alpha-olefins using a catalyst comprising certainmetallocene/alumoxane systems.

European Patent Publication 305,022-Al to Mitsui Petrochemical relatesto certain synthetic hydrocarbon lubricating oil compositions containinga load-withstanding additive and a liquid ethylene alpha-olefin randomcopolymer modified by graft copolymerization with an unsaturatedcarboxylic acid or derivative thereof (e.g., maleic anhydride). Theethylene alpha-olefin copolymers (M_(n) of 300 to 12,000) are obtainedusing Ziegler catalysts (e.g., catalyst formed from soluble V compoundand an organo aluminum compound), are grafted in the presence of a freeradical initiator.

PCT Published Patent Application WO 88/01626 relates to transition metalcompound/alumoxane catalysts for polymerizing alpha-olefins.

SUMMARY OF THE INVENTION

The present invention is directed to an oil-soluble fuel and lubricatingoil additive comprising ethylene alpha-olefin interpolymers of 300 to20,000 number average molecular weight terminally substituted withamines, wherein the ethylene alpha-olefin polymer group is derived froma terminally unsaturated ethylene alpha-olefin polymer wherein theterminal unsaturation comprises ethenylidene unsaturation. Theamine-substituted polymers of this invention are useful per se asadditives to fuels and lubricating oils.

The materials of the invention are different from the prior art becauseof their effectiveness and their ability to provide enhanced lubricatingoil dispersancy, as exhibited by their enhanced sludge and varnishcontrol properties. In fuels, the additives serve to minimize the degreeof carburetor and intake valve fouling from deposits. In addition, theadditives of this invention possess superior viscometric properties.

The process of this invention permits the preparation of lubricating oiland fuel dispersant additives which are simultaneously characterized bya high active ingredient content (usually at least about 60 wt.%, up toabout 95 wt.%) and by advantageous viscosity properties to permit theadditives to be readily handled. In addition, the amine-substitutedethylene alpha-olefin polymers of this invention can be characterized byVR values (as hereinafter defined) of not greater than about 4.1,thereby providing advantageous viscosity modifying properties to thelubricating oils containing them. The present invention can produce suchsubstituted polymers in a more highly concentrated form than prior artmaterials, thereby reducing the possible processing difficulties whichare associated with less concentrated fuel and halogen-containinglubricating oil additives.

Further, dispersant materials can be prepared from the substitutedpolymers of this invention to provide fuel and lubricating oildispersant products having VR' values of not greater than about 4.1 andVR'/VR_(r) ratios of less than about 1.11 (as such values and ratios arehereinafter defined). Surprisingly, the process of this inventionpermits the preparation of highly concentrated dispersants from highmolecular weight ethylene-alpha-olefin polymers (Mn>5,000, e.g.,5,500-20,000) of superior viscosity properties.

In distillate fuels, the dispersant materials of this invention canreduce the formation of intake valve deposits in an internal combustionengine while minimizing valve sticking and crankcase oil thickening.

DETAILED DESCRIPTION OF THE INVENTION Preparation of EthyleneAlpha-olefin Polymer

The polymers employed in this invention are polymers of ethylene and atleast one alpha-olefin having the formula H₂ C═CHR¹ wherein R¹ isstraight chain or branched chain alkyl radical comprising 1 to 18 carbonatoms and wherein the polymer contains a high degree of terminalethenylidene unsaturation. Preferably R¹ in the above formula is alkylof from 1 to 8 carbon atoms, and more preferably is alkyl of from 1 to 2carbon atoms. Therefore, useful comonomers with ethylene in thisinvention include propylene, 1-butene, hexene-1, octene-1,4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1,pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1and mixtures thereof (e.g., mixtures of propylene and 1-butene, and thelike).

Exemplary of such polymers are ethylene-propylene copolymers,ethylene-butene-1 copolymers and the like. Preferred polymers arecopolymers of ethylene and propylene and ethylene and butene-1.

The molar ethylene content of the polymers employed in this invention ispreferably in the range of between about 20 and about 80 percent, andmore preferably between about 30 and about 70 percent. When propyleneand/or butene-1 are employed as comonomer(s) with ethylene, the ethylenecontent of such copolymers is most preferably between about 45 and about65 percent, although higher or lower ethylene contents may be present.

The polymers employed in this invention generally possess a numberaverage molecular weight of from about 300 to about 20,000 (e.g., from300 to 10,000), preferably from about 900 to 20,000; more preferably offrom about 900 to 10,000 (e.g., from about 700 to about 15,000); fromabout 1500 to about 5,000. Polymers having a number average molecularweight within the range of from about 700 to 5,000 (e.g., 1500 to 3,000)are particularly useful in the present invention. The number averagemolecular weight for such polymers can be determined by several knowntechniques. A convenient method for such determination is by sizeexclusion chromatography (also known as gel permeation chromatography(GPC)) which additionally provides molecular weight distributioninformation, see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern SizeExclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.

Consequently, such polymers generally possess an gintrinsic viscosity(as measured in tetralin at 135° C.) of between about 0.025 and about0.9 dl/g, preferably of between about 0.05 and about 0.5 dl/g, mostpreferably of between about 0.075 and about 0.4 dl/g.

The polymers employed in this invention preferably exhibit a degree ofcrystallinity such that, when grafted, they are essentially amorphous.

The polymers employed in this invention are further characterized inthat up to about 95% and more of the polymer chains possess terminalethenylidene-type unsaturation. Thus, one end of such polymers will beof the formula POLY-C(T¹)=CH₂ wherein T¹ is C₁ to C₁₈ alkyl, preferablyC₁ to C₈ alkyl, and more preferably C₁ to C₂ alkyl, (e.g., methyl orethyl) and wherein POLY represents the polymer chain. The chain lengthof the T¹ alkyl group will vary depending on the comonomer(s) selectedfor use in the polymerization. A minor amount of the polymer chains cancontain terminal ethenyl unsaturation, i.e. POLY-CH═CH₂, and a portionof the polymers can contain internal monounsaturation, e.g.POLY-CH═CH(T¹), wherein T¹ is as defined above.

The polymer employed in this invention comprises polymer chains, atleast about 30 percent of which possess terminal ethenylideneunsaturation. Preferably at least about 50 percent, more preferably atleast about 60 percent, and most preferably at least about 75 percent(e.g. 75-98%), of such polymer chains exhibit terminal ethyenylideneunsaturation. The percentage of polymer chains exhibiting terminalethyenylidene unsaturation may be determined by FTIR spectroscopicanalysis, titration, or C¹³ NMR.

The polymer and the composition employed in this invention may beprepared as described in U.S. Pat. No. 4,668,834, in European PatentPublications 128,046 and 129,368, and in co-pending Ser. No. 728,111,filed Apr. 29, 1985, and copending Ser. No. 93,460, filed Sept. 10,1987, the disclosures of all of which are hereby incorporated byreference in their entirety.

The polymers for use in the present invention can be prepared bypolymerizing monomer mixtures comprising ethylene in combination withother monomers such as alpha-olefins having from 3 to 20 carbon atoms(and preferably from 3-4 carbon atoms, i.e., propylene, butene-1, andmixtures thereof) in the presence of a catalyst system comprising atleast one metallocene (e.g., a cyclopentadienyl-transition metalcompound) and an alumoxane compound. The comonomer content can becontrolled through the selection of the metallocene catalyst componentand by controlling the partial pressure of the various monomers.

The catalysts employed in the production of the reactant polymers areorganometallic coordination compounds which are cyclopentadienylderivatives of a Group 4b metal of the Periodic Table of the Elements(56th Edition of Handbook of Chemistry and Physics, CRC Press [1975])and include mono, di and tricyclopentadienyls and their derivatives ofthe transition metals. Particularly desirable are the metallocene of aGroup 4b metal such as titanium, zirconium, and hafnium. The alumoxanesemployed in forming the reaction product with the metallocenes arethemselves the reaction products of an aluminum trialkyl with water.

In general, at least one metallocene compound is employed in theformation of the catalyst. As indicated, supra, metallocene is a metalderivative of a cyclopentadiene. The metallocenes usefully employed inaccordance with this invention contain at least one cyclopentadienering. The metal is selected from the Group 4b preferably titanium,zirconium, and hafnium, and most preferably hafnium and zirconium. Thecyclopentadienyl ring can be unsubstituted or contain one or moresubstituents (e.g., from 1 to 5 substituents) such as, for example, ahydrocarbyl substituent (e.g., up to 5 C₁ to C₅ hydrocarbylsubstituents) or other substituents, e.g. such as, for example, atrialkyl silyl substituent. The metallocene can contain one, two, orthree cyclopentadienyl rings; however, two rings are preferred.

Useful metallocenes can be represented by the general formulas:

    (Cp).sub.m MR.sub.n X.sub.q                                I.

wherein Cp is a cyclopentadienyl ring, M is a Group 4b transition metal,R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20carbon atoms, X is a halogen, and m is a whole number from 1 to 3, n isa whole number from 0 to 3, and q is a whole number from 0 to 3.

    (C.sub.5 R'.sub.k).sub.g R".sub.s (C.sub.5 R'.sub.k)MQ.sub.3-g II

    and

    R".sub.s (C.sub.5 R'.sub.k).sub.2 MQ'                      III.

wherein (C₅ R'_(k)) is a cyclopentadienyl or substitutedcyclopentadienyl, each R' is the same or different and is hydrogen or ahydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, orarylalkyl radical containing from 1 to 20 carbon atoms, a siliconcontaining hydrocarbyl radical, or hydrocarbyl radicals wherein twocarbon atoms are Joined together to form a C₄ -C₆ ring, R" i s a C₁ -C₄alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphineor amine radical bridging two (C₅ R'_(k)) rings, Q is a hydrocarbylradical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radicalhaving from 1-20 carbon atoms, hydrocarboxy radical having from 1-20carbon atoms or halogen and can be the same or different from eachother, Q' is an alkylidene radical having from 1 to about 20 carbonatoms, s is 0 or 1, g is 0, 1 or 2, s is 0 when g is 0, k is 4 when s is1, and k is 5 when s is 0, and M is as defined above. Exemplaryhydrocarbyl radicals are methyl, ethyl, propyl, butyl, amyl, isoamyl,hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl,phenyl and the like. Exemplary silicon containing hydrocarbyl radicalsare trimethylsilyl, triethylsilyl and triphenylsilyl. Exemplary halogenatoms include chlorine, bromine, fluorine and iodine and of thesehalogen atoms, chlorine is preferred. Exemplary hydrocarboxy radicalsare methoxy ethoxy, butoxy, amyloxy and the like. Exemplary of thealkylidene radicals is methylidene, ethylidene and propylidene.

Illustrative, but non-limiting examples of the metallocenes representedby formula I are dialkyl metallocenes such asbis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titaniumdiphenyl, bis(cyclopentadienyl)zirconium dimethyl,bis(cyclopentadieny)zirconium diphenyl, bis(cyclopentadienyl)hafniumdimethyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl,bis(cyclopentadienyl)zirconium di-neopentyl,bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)vanadium dimethyl; the mono alkylmetallocenes such as bis(cyclopentadienyl)titanium methyl chloride,bis(cyclopentadienyl) titanium ethyl chloridebis(cyclopentadienyl)titanium phenyl chloride,bis(cyclopentadienyl)zirconium hydrochloride,bis(cyclopentadienyl)zirconium methyl chloride,bis(cyclopentadienyl)zirconium ethyl chloride,bis(cyclopentadienyl)zirconium phenyl chloride,bis(cyclopentadienyl)titanium methyl bromide,bis(cyclopentadienyl)titanium methyl iodide,bis(cyclopentadienyl)titanium ethyl bromide,bis(cyclopentadienyl)titanium ethyl iodide,bis(cyclopentadienyl)titanium phenyl bromide,bis(cyclopentadienyl)titanium phenyl iodide,bis(cyclopentadienyl)zirconium methyl bromide,bis(cyclopentadienyl)zirconium methyl iodide,bis(cyclopentadienyl)zirconium ethyl bromide.bis(cyclopentadienyl)zirconium ethyl iodide,bis(cyclopentadienyl)zirconium phenyl bromide,bis(cyclopentadienyl)zirconium phenyl iodide; the trialkyl metallocenessuch as cyclopentadienyltitanium trimethyl, cyclopentadienyl zirconiumtriphenyl, and cyclopentadienyl zirconium trineopentyl,cyclopentadienylzirconium trimethyl, cyclopentadienylhafnium triphenyl,cyclopentadienylhafnium trineopenty, and cyclopentadienylhafniumtrimethyl.

Illustrative, but non-limiting examples of II and III metallocenes whichcan be usefully employed are monocyclopentadienyls titanocenes such as,pentamethylcyclopentadienyl titanium trichloride,pentaethylcyclopentadienyl titanium trichloride,bis(pentamethylcyclopentadienyl) titanium diphenyl, the carbenerepresented by the formula bis(cyclopentadienyl)titanium=CH₂ andderivatives of this reagent such asbis(cyclopentadienyl)Ti=CH₂.Al(CH₃)₃, (Cp₂ TiCH₂)₂, Cp₂ TiCH₂CH(CH₃)CH₂, Cp₂ Ti-CH₂ CH₂ CH₂ ; substituted bis (Cp)Ti (IV) compoundssuch as bis(indenyl) titanium diphenyl or dichloride,bis(methylcyclopentadienyl)titanium diphenyl or dihalides; dialkyl,trialkyl, tetra-alkyl and penta-alkyl cyclopentadienyl titaniumcompounds such as bis(1,2-dimethylcyclopentadienyl)titanium diphenyl ordichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl ordichloride and other dihalide complexes; silicon, phosphine, amine orcarbon bridged cyclopentadiene complexes, such asdimethylsilyldicyclopentadienyl titanium diphenyl or dichloride, methylphosphine dicyclopentadienyl titanium diphenyl or dichloride,methylenedicyclopentadienyl titanium diphenyl or dichloride and othercomplexes described by formulae II and III.

Illustrative but non-limiting examples of the zirconocenes of Formula IIand III which can be usefully employed are, pentamethylcyclopentadienylzirconium trichloride, pentaethylcyclopentadienyl zirconium trichloride,the alkyl substituted cyclopentadienes, such asbis(ethylcyclopentadienyl) zirconium dimethyl,bis(beta-phenylpropylcyclopentadienyl) zirconium dimethyl,bis(methylcycl opentadienyl) zirconium dimethyl,bis(n-butylcyclopentadienyl)zirconium dimethylbis(cyclohexylmethylcyclopentadienyl)zirconium dimethylbis(n-octyl-cyclopentadienyl)zirconium dimethyl, and haloalkyl anddihydride, and dihalide complexes of the above; dialkyl, trialkyl,tetra-alkyl, and penta-alkyl cyclopentadienes, such asbis(pentamethylcyclopentadienyl)zirconium diphenyl,bis(pentamethylcyclopentadienyl)zirconium dimethyl,bis(1,2-dimethylcyclopentadienyl)zirconium dimethyl and mono anddihalide and hydride complexes of the above; silicon, phosphorus, andcarbon bridged cyclopentadiene complexes such asdimethylsilyldicyclopentadienyl zirconium dimethyl, methyl halide ordihalide, and methylene dicyclopentadienyl zirconium dimethyl, methylhalide, or dihalide. Mono, di and tri-silyl substituted cyclopentadienylcompounds such as bis(trimethylsilylcyclopentadienyl)zirconiumdichloride and dimethyl bis(1,3-di-trimethylsilylcyclopentadienyl)zirconium dichloride and dimethyl andbis(1,2,4-tri-trimethylsilylcyclopentadienyl)zirconium dichloride anddimethyl. Carbenes represented by the formulae Cp₂ Zr=CH₂ P(C₆ H₅)₂ CH₃,and derivatives of these compounds such as Cp₂ ZrCH₂ CH(CH₃)CH₂.

Mixed cyclopentadienyl metallocene compounds such as cyclopentadienyl(pentamethyl cyclopentadienyl)zirconium dichloride,(1,3-di-trimethylsilylcyclopentadienyl) (pentamethylcyclopentadienyl)zirconium dichloride, and cyclopentadienyl(indenyl) zirconium dichloridecan be employed.

Most preferably, the polymers used in this invention are substantiallyfree of ethylene homopolymer.

Bis (cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)hafnium;dimethyl, bis(cyclopentadienyl) vanadium dichloride and the like areillustrative of other metallocenes.

Some preferred metallocenes are bis(cyclopentadienyl)zirconium;dimethyl, bis(cyclopentadienyl)zirconium dichloride;bis(cyclopentadienyl)titanium dichloride; bis(methylcyclopentadienyl)zirconium dichloride; bis(methylcyclopentadienyl)titanium dichloride;bis(n-butylcyclopentadienyl) zirconium dichloride;dimethylsilyldicyclopentadienyl zirconium dichloride;bis(trimethylsilycyclopentadienyl)zirconium dichloride; anddimethylsilyldicyclopentadienyl titanium dichloride;bis(indenyl)zirconium dichloride;bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; the racemic and/ormeso isomer of 1,2-ethylene-bridgedbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; the racemic and/ormeso isomer of 1,1-dimethylsilyl-bridgedbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride; and the racemicand/or meso isomer of 1,1-dimethylsilyl-bridgedbis(methylcyclopentadienyl)zirconium dichloride.

The alumoxane compounds useful in the polymerization process may becyclic or linear. Cyclic alumoxanes may be represented by the generalformula (R--Al--O)_(n) while linear alumoxanes may be represented by thegeneral formula R(R--Al--O)n'AlR₂. In the general formula R is a C₁ -C₅alkyl group such as, for example, methyl, ethyl, propyl, butyl andpentyl, n is an integer of from 3 to 20, and n' is an integer from 1 toabout 20. Preferably, R is methyl and n and n' are 4-18. Generally, inthe preparation of alumoxanes from, for example, aluminum trimethyl andwater, a mixture of the linear and cyclic compounds is obtained.

The alumoxane can be prepared in various ways. Preferably, they areprepared by contacting water with a solution of aluminum trialkyl, suchas, for examples, aluminum trimethyl, in a suitable organic solvent suchas toluene or an aliphatic hydrocarbon. For example, the aluminum alkylis treated with water in the form of a moist solvent. In an alternativemethod, the aluminum alkyl such as aluminum trimethyl can be desirablycontacted with a hydrated salt such as hydrated copper sulfate orferrous sulfate. Preferably, the alumoxane is prepared in the presenceof a hydrated ferrous sulfate. The method comprises treating a dilutesolution of aluminum trimethyl in, for example, toluene, with ferroussulfate represented by the general formula FeSO₄.7H₂ O. The ratio offerrous sulfate to aluminum trimethyl is desirably about 1 mole offerrous sulfate for 6 to 7 moles of aluminum trimethyl. The reaction isevidenced by the evolution of methane.

The mole ratio of aluminum in the alumoxane to total metal in themetallocenes which can be usefully employed can be in the range of about0.5:1 to about 1000:1, and desirably about 1:1 to about 100:1.Preferably, the mole ratio will be in the range of 50:1 to about 5:1 andmost preferably 20:1 to 5:1.

The solvents used in the preparation of the catalyst system are inerthydrocarbons, in particular a hydrocarbon that is inert with respect tothe catalyst system. Such solvents are well known and include, forexample, isobutane, butane, pentane, hexane, heptane, octane,cyclohexane, methylcyclohexane, toluene, xylene and the like.

Polymerization is generally conducted at temperatures ranging betweenabout 20° and about 300° C., preferably between about 30° and about 200°C. Reaction time is not critical and may vary from several hours or moreto several minutes or less, depending upon factors such as reactiontemperature, the monomers to be copolymerized, and the like. One ofordinary skill in the art may readily obtain the optimum reaction timefor a given set of reaction parameters by routine experimentation.

The catalyst systems described herein are suitable for thepolymerization of olefins in solution over a wide range of pressures.Preferably, the polymerization will be completed at a pressure of fromabout 10 to about 3,000 bar, and generally at a pressure within therange from about 40 bar to about 2,000 bar, and most preferably, thepolymerization will be completed at a pressure within the range fromabout 50 bar to about 1,500 bar.

After polymerization and, optionally, deactivation of the catalyst(e.g., by conventional techniques such as contacting the polymerizationreaction medium with water or an alcohol, such as methanol, propanol,isopropanol, etc., or cooling or flashing the medium to terminate thepolymerization reaction), the product polymer can be recovered byprocesses well known in the art. Any excess reactants may be flashed offfrom the polymer.

The polymerization may be conducted employing liquid monomer, such asliquid propylene, or mixtures of liquid monomers (such as mixtures ofliquid propylene and 1-butene), as the reaction medium. Alternatively,polymerization may be accomplished in the presence of a hydrocarboninert to the polymerization such as butane, pentane, isopentane, hexane,isooctane, decane, toluene, xylene, and the like.

In those situations wherein the molecular weight of the polymer productthat would be produced at a given set of operating conditions is higherthan desired, any of the techniques known in the prior art for controlof molecular weight, such as the use of hydrogen and/or polymerizationtemperature control, may be used in the process of this invention. If sodesired, the polymerization may be carried out in the presence ofhydrogen to lower the polymer molecular weight. Care should be taken toassure that terminal ethenylidene unsaturation is not reduced to lessthan about 30 percent of the polymer chains.

However, the polymers are preferably formed in the substantial absenceof added H₂ gas, that is, the absence of H₂ gas added in amountseffective to substantially reduce the polymer molecular weight. Morepreferably, the polymerizations will be conducted employing less than 5wppm, and more preferably less than 1 wppm, of added H₂ gas, based onthe moles of the ethylene monomer charged to the polymerization zone.

When carrying out the polymerization in a batch-type fashion, thereaction diluent (if any), ethylene and alpha-olefin comonomer(s) arecharged at appropriate ratios to a suitable reactor. Care must be takenthat all ingredients are dry, with the reactants typically being passedthrough molecular sieves or other drying means prior to theirintroduction into the reactor. Subsequently, either the catalyst andthen the cocatalyst, or first the cocatalyst and then the catalyst areintroduced while agitating the reaction mixture, thereby causingpolymerization to commence. Alternatively, the catalyst and cocatalystmay be premixed in a solvent and then charged to the reactor. As polymeris being formed, additional monomers may be added to the reactor. Uponcompletion of the reaction, unreacted monomer and solvent are eitherflashed or distilled off, if necessary by vacuum, and the low molecularweight copolymer withdrawn from the reactor.

The polymerization may be conducted in a continuous manner bysimultaneously feeding the reaction diluent (if employed), monomers,catalyst and cocatalyst to a reactor and withdrawing solvent, unreactedmonomer and polymer from the reactor so as to allow a residence time ofingredients long enough for forming polymer of the desired molecularweight and separating the polymer from the reaction mixture.

Preparation of Halogenated Ethylene Alpha-olefin Polymer

The halogenated ethylene alpha-olefin polymer can be prepared bycontacting the polymer with halogen (as shown in U.S. Pat. Nos.3,275,554; 3,438,757, 3,565,804; and 4,000,353, the disclosures of whichare hereby incorporated by reference in their entirety). The halogengroup on the halogenated polymer is displaced with thenitrogen-containing compound in the subsequent reaction therewith.

For example, an ethylene alpha-olefin, wherein the polymer has anaverage molecular weight within the range of from 300 to about 20,000,is halogenated with either bromine or chlorine; preferably the latter.The halogen may be conveniently added as gaseous chloride, liquidbromine, or a hydrohalogen, e.g., HCl or HBr gas.

The amount of halogen introduced will depend on the particularhydrocarbon used, the desired amount of amine to be introduced into themolecule, the particular alkylene amine used, and the halogen used. Theamount of halogen introduced will generally be in the range from about 1to 5 halogen atoms per molecule, depending on the reactivity of theresulting halide. On a weight percent basis, the amount of halide willgenerally range from about 1 to 25, more usually from about 1 to 10.

The halogenation step may be conducted in the temperature range of fromabout ordinary ambient temperatures to about 120° C. To aid in thehalogenation step, the polymer may be dissolved in a suitable solvent,such as carbon tetrachloride, in order to lower the viscosity of thepolymer, although the use of such a solvent is not necessary.

The time required for halogenation may be varied to some extent by therate at which the halogen is introduced. Ordinarily from about 2 toabout 5 hours is a satisfactory halogenation period.

The reaction product mixture comprising the desired halogenatedethylene-alpha-olefin polymer (e.g., chlorinated ethylene-propylenepolymer) will generally contain unreacted polymer, (that is, polymerwhich is unsubstituted by halogen), in a concentration of less thanabout 40 wt.% (e.g., from 5 to 35 wt.%), more preferably less than about30 wt.% (e.g., from 10 to 25 wt.%) and will be generally characterizedby a VR value ("viscosity ratio" value) of not greater than about 4.1,usually not greater than about 4.0, preferably from about 2.0 to 3.9,and most preferably from about 3.0 to 3.8. As used herein, the term "VRvalue" is intended to mean quotient determine by the expression (IV):##EQU1## wherein VISa is the kinematic viscosity (KV) of the halogenatedpolymer reaction product mixture at 100° C. in units of centistokes (asdetermined by ASTM Method No. D445) and VISb is the cold crankingsimulator (CCS) viscosity of the ene reaction product mixture at -20° C.in units of poise (as determined by ASTM Method No. D2602), wherein themeasurements are made upon a 2 wt.% solution of the halogenated polymerreaction product mixture in an oil (herein termed the "reference oil")comprising S150N (solvent 150 neutral) mineral lubricating oil (ExxonCompany U.S.A.), wherein the such reference oil is characterized by anASTM D445 kinematic viscosity of 5.2 cSt (100° C.) and an ASTM D2602 CCSviscosity of 19.2 poise (±0.4 poise) (at -20° C.). The "VRr" value ofthe reference oil will then be about 3.7±0.1.

It will be understood that the ethylene alpha-olefin polymers of thisinvention which are charged to the halogenation reaction zone can becharged alone or together with (e.g., in admixture with) otherpolyalkenes derived from alkenes having from 1 to 20 carbon atoms(butene, pentene, octene, decene, dodecene, tetradodecene and the like)and homopolymers of C₃ to C₁₀, e.g., C₂ to C₅, monoolefins, andcopolymers of C₂ to C₁₀, e.g., C₂ to C₅, monoolefins, said additionalpolymer having a number average molecular weight of at least about 900,and a molecular weight distribution of less than about 4.0, preferablyless than about 3.0 (e.g, from 1.2 to 2.8). Preferred such additionalolefin polymers comprise a major molar amount of C₂ to C₁₀, e.g., C₂ toC₅ monoolefin. Such olefins include ethylene, propylene, butylene,isobutylene, pentene, octene-1, styrene, etc. Exemplary of theadditionally charged homopolymers is polypropylene, polyisobutylene, andpoly-n-butene the like as well as interpolymers of two or more of sucholefins such as copolymers of: ethylene and propylene (prepared byconventional methods other than as described above for the preferredethylene alpha-olefin copolymers employed in this invention, that is,ethylene-propylene copolymers which are substantially saturated, whereinless than about 10 wt% of the polymer chains contain ethylenicunsaturation); butylene and isobutylene; propylene and isobutylene; etc.Other copolymers include those in which a minor molar amount of thecopolymer monomers, e.g., 1 to 10 mole %, is a C₄ to C₁₈ non-conjugateddiolefin, e.g., a copolymer of isobutylene and butadiene: or a copolymerof ethylene, propylene and 1,4-hexadiene; etc. The additional sucholefin polymers charged to the reaction will usually have number averagemolecular weights of at least about 900, more generally within the rangeof about 1200 and about 5,000, more usually between about 1500 and about4000. Particularly useful such additional olefin polymers have numberaverage molecular weights within the range of about 1500 and about 3000with approximately one double bond per chain. An especially usefuladditional such polymer is polyisobutylene. Preferred are mixtures ofsuch polyisobutylene with ethylene-propylene copolymers wherein at least30 wt% of the copolymer chains contain terminal ethenylidenemonounsaturation as described above.

The number average molecular weight for such polymers can be determinedby several known techniques. A convenient method for such determinationis by gel permeation chromatography (GPC) which additionally providesmolecular weight distribution information, see W. W. Yau, J. J. Kirklandand D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wileyand Sons, New York, 1979.

Preparation of Amine-substituted Polymer Products

While not wishing to bound therby, it is believed the halogenation ofthe ethylene alpha-olefin polymers used in the present invention,because of their high concentration of polymer chains (up to 90% andmore) having terminal ethenylidene unsaturation, leads to halogentedpolymer chains wherein the halide group is also substantially terminal(that is, wherein the halide group is attached to either the chain andcarbon or to a pendant carbon attached to the beta-carbon of the chain).This can be illustrated as follows, employing an ethylene-propylenecopolymer (EP) and chlorine for example: ##STR1## Halogenation isbelieved to result in a mixture of products of which the Clmono-terminally substituted polymer is the majority. It is believed form(i) is the major halogenated polymer product, and that form (ii) isproduced in the product mixture in lesser concentrations. Form (iii),which is Cl di-substituted illustrates a possible by-product.

Reaction of the halogenated polymer with an amine, e.g., ethylenediamine, will result in a mixture of products formed via EP-nitrogenbonds, and elimination of HCl, and can be illustrated as follows:##STR2## wherein (iv), (v) and (vi) are formed from halogenated products(i), (ii) and (iii), respectively.

However, the above halogenated and aminated EP products are illustrativeand are not the only forms which can be envisioned.

The halogenated polymers prepared as described above, can be contactedwith one or more amines to form the novel dispersants of this invention.

Amine compounds useful for reaction with the halogenated polymer includemono- and (preferably) polyamines, of about 2 to 60, preferably 2 to 40(e.g. 3 to 20), total carbon atoms and about 1 to 12, preferably 3 to12, and most preferably 3 to 9 nitrogen atoms in the molecule. Theseamines may be hydrocarbyl amines or may be hydrocarbyl amines includingother groups, e.g, hydroxy groups, alkoxy groups, amide groups,nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6hydroxy groups, preferably 1 to 3 hydroxy groups are particularlyuseful. Preferred amines are aliphatic saturated amines, including thoseof the general formulas: ##STR3## wherein R, R', R'' and R''' areindependently selected from the group consisting of hydrogen; C₁ to C₂₅straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy C₂ to C₆alkylene radicals; C₂ to C₁₂ hydroxy amino alkylene radicals; and C₁ toC₁₂ alkylamino C₂ to C₆ alkylene radicals; and wherein R''' canadditionally comprise a moiety of the formula: ##STR4## wherein R' is asdefined above, and wherein r and r' can be the same or a differentnumber of from 2 to 6, preferably 2 to 4; and t and t' can be the sameor different and are numbers of from 0 to 10, preferably 2 to 7, andmost preferably about 3 to 7, with the proviso that the sum of t and t'is not greater than 15. To assure a facile reaction, it is preferredthat R, R', R'', R''', r, r', t and t' be selected in a mannersufficient to provide the compounds of Formulas Va and Vb with typicallyat least one primary or secondary amine group, preferably at least twoprimary or secondary amine groups. This can be achieved by selecting atleast one of said R, R', R'' or R''' groups to be hydrogen or by lettingt in Formula Vb be at least one when R''' is H or when the VI moietypossesses a secondary amino group. The most preferred amine of the aboveformulas are represented by Formula Vb and contain at least two primaryamine groups and at least one, and preferably at least three, secondaryamine groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene)triamine;di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine; N,N-d i(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine; N-dodecyl-1,3-propanediamine; tris hydroxymethylaminomethane (THAM); diisopropanol amine:diethanol amine; triethanol amine; mono-, di-, and tri-tallow amines;amino morpholines such as N-(3-aminopropyl)morpholine; and mixturesthereof.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula (VII): ##STR5## wherein p₁ and p₂ are the same or different andare each integers of from 1 to 4, and n₁, n₂ and n₃ are the same ordifferent and are each integers of from 1 to 3. Non-limiting examples ofsuch amines include 2-pentadecy imidazoline; N-(2-aminoethyl)piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. Low costpoly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms permolecule are available commercially under trade names such as "PolyamineH", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formula (VIII): ##STR6## where m has a value of about 3 to 70 andpreferably 10 to 35; and the formula (IX): ##STR7## where n''' has avalue of about 1 to 40 with the provision that the sum of all the n'''values is from about 3 to about 70 and preferably from about 6 to about35, and R⁴ is a polyvalent saturated hydrocarbon radical of up to tencarbon atoms wherein the number of substituents on the R⁴ group isrepresented by the value of "a", which is a number of from 3 to 6. Thealkylene groups in either formula (VIII) or (IX) may be straight orbranched chains containing about 2 to 7, and preferably about 2 to 4carbon atoms.

The polyoxyalkylene polyamines of formulas (VIII) or (IX) above,preferably polyoxyalkylene diamines and polyoxyalkylene triamines, mayhave average molecular weights ranging from about 200 to about 4000 andpreferably from about 400 to about 2000. The preferred polyoxyalkylenepolyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.

A particularly useful class of amines are the polyamido and relatedamines disclosed in U.S. Pat. No. 4,857,217 (the disclosure of which ishereby incorporated by reference in its entirety), which comprisereaction products of a polyamine and an alpha, beta unsaturated compoundof the formula: ##STR8## wherein X is sulfur or oxygen, Y is --OR⁸,--SR⁸, or --NR⁸ (R⁹) , and R⁵, R⁶, R⁷, R⁸ a nd R9 are the same ordifferent and are hydrogen or substituted or unsubstituted hydrocarbyl.Any polyamine, whether aliphatic, cycloaliphatic, aromatic,heterocyclic, etc., can be employed provided it is capable of addingacross the acrylic double bond and amidifying with for example thecarbonyl group (--C(O)--) of the acrylate-type compound of formula X, orwith the thiocarbonyl group (--C(S)--) of the thioacrylate-type compoundof formula X.

When R⁵, R⁶, R⁷, R⁸ or R⁹ in Formula X are hydrocarbyl, these groups cancomprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic,which can be substituted with groups which are substantially inert toany component of the reaction mixture under conditions selected forpreparation of the amido-amine. Such substituent groups include hydroxy,halide (e.g., Cl, Fl, I, Br), --SH and alkylthio. When one or more of R⁵through R⁹ are alkyl, such alkyl groups can be straight or branchedchain, and will generally contain from 1 to 20, more usually from 1 to10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkylgroups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. Whenone or more of R⁵ through R⁹ are aryl, the aryl group will generallycontain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).

When one or more of R⁵ through R⁹ are alkaryl, the alkaryl group willgenerally contain from about 7 to 20 carbon atoms, and preferably from 7to 12 carbon atoms. Illustrative of such alkaryl groups are tolyl,m-ethylphenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R⁵through R⁹ are aralkyl, the aryl component generally consists of phenylor (C₁ to C₆) alkyl-substituted phenol and the alkyl component generallycontains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbonatoms. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and4-isobutylbenzyl. When one or more of R⁵ and R⁹ are cycloalkyl, thecycloalkyl group will generally contain from 3 to 12 carbon atoms, andpreferably from 3 to 6 carbon atoms. Illustrative of such cycloalkylgroups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, andcyclododecyl. When one or more of R⁵ through R⁹ are heterocyclic, theheterocyclic group generally consists of a compound having at least onering of 6 to 12 members in which on or more ring carbon atoms isreplaced by oxygen or nitrogen. Examples of such heterocyclic groups arefuryl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyland 1,4-oxazinyl.

The alpha, beta ethylenically unsaturated carboxylate compounds employedherein have the following formula: ##STR9## wherein R⁵, R⁶, R⁷, and R⁸are the same or different and are hydrogen or substituted orunsubstituted hydrocarbyl as defined above. Examples of such alpha,beta-ethylenically unsaturated carboxylate compounds of formula XI areacrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl,and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid,2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid,3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid,3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid,2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid,2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid,2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate,methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate,dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl3-phenyl-2-propenoate, and the like.

The alpha, beta ethylenically unsaturated carboxylate thioestercompounds employed herein have the following formula: ##STR10## whereinR⁵, R⁶, R⁷, and R⁸ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofsuch alpha, beta-ethylenically unsaturated carboxylate thioesters offormula XII are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate,isopropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiarybutylmercapto 2-propenoate, octadecylmercapto 2-propenoate,dodecylmercapto 2-decenoate, cyclopropylmercapto2,3-dimethyl-2-butenoate, methylmercapto 3-phenyl-2-propenoate,methylmercapto 2-propenoate, methylmercapto 2-methyl-2-propenoate, andthe like.

The alpha, beta ethylenically unsaturated carboxyamide compoundsemployed herein have the following formula: ##STR11## where in R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated carboxyamides of formula XIII are2-butenamide, 2-hexenamide, 2-decenamide, 3-methyl-2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide,2-methyl-2-butenamide, 2-propyl-2-propenamide, 2-isopropyl-2-hexenamide,2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl2-butenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexenamide,N-isopropyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl2-propenamide, N-octadecyl 2-propenamide, N-N-didodecyl 2-decenamide,N-cyclopropyl 2,3-dimethyl-2-butenamide, N-methyl3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-propenamide,2-ethyl-2-propenamide and the like.

The alpha, beta ethylenically unsaturated thiocarboxylate compoundsemployed herein have the following formula: ##STR12## wherein R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated thiocarboxylate compounds of formula XIVare 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid,3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid,3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid,2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid,2-isopropyl-2-hexenthioic acid, 2,3-dimethyl-2-butenthioic acid,3-cyclohexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenthioate,ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate,tertiary butyl 2-propenthioate, octadecyl 2-propenthioate, dodecyl2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl3-phenyl-2-propenthioate, and the like.

The alpha, beta ethylenically unsaturated dithioic acid and acid estercompounds employed herein have the following formula: ##STR13## whereinR⁵, R⁶, R⁷, and R⁸ are the same or different and are hydrogen orsubstituted or unsubstituted hydrocarbyl as defined above. Examples ofalpha, beta-ethylenically unsaturated dithioic acids and acid esters offormula XV are 2-butendithioic acid, 2-hexendithioic acid,2-decendithioic acid, 3-methyl-2-heptendithioic acid,3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid,3-cyclohexyl-2-butendithioic acid, 2-methyl-2-but endithioic acid,2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid,2,3-dimethyl-2-butendithioic acid,3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid,methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate,phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl2-propendithioate, dodecyl 2-decendithioate, cyclopropyl2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate, andthe like.

The alpha, beta ethylenically unsaturated thiocarboxyamide compoundsemployed herein have the following formula: ##STR14## wherein R⁵, R⁶,R⁷, R⁸ and R⁹ are the same or different and are hydrogen or substitutedor unsubstituted hydrocarbyl as defined above. Examples of alpha,beta-ethylenically unsaturated thiocarboxyamides of formula XVI are2-butenthioamide, 2-hexenthioamide, 2-decenthioamide,3-methyl-2-heptenthioamide, 3-methyl-2-butenthioamide,3-phenyl-2-propenthioamide, 3-cyclohexyl-2-butenthioamide,2-methyl-2-butenthioamide, 2-propyl-2-propenthioamide,2-isopropyl-2-hexenthioamide, 2,3-dimethyl-2-butenthioamide,3-cyclohexyl-2 -methyl-2 -pententhioamide, N-methyl 2-butenthioamide,N,N-diethyl 2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl2-propenthioamide, N-N-didodecyl 2-decenthioamide, N-cyclopropyl2,3-dimethyl-2-butenthioamide, N-methyl 3-phenyl-2-propenthioamide,2-propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-propenthioamideand the like.

Preferred compounds for reaction with the polyamines in accordance withthis invention are lower alkyl esters of acrylic and (lower alkyl)substituted acrylic acid. Illustrative of such preferred compounds arecompounds of the formula: ##STR15## where R⁷ is hydrogen or a C₁ to C₄alkyl group, such as methyl, and R⁸ is hydrogen or a C₁ to C₄ alkylgroup, capable of being removed so as to form an amido group, forexample, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,aryl, hexyl, etc. In the preferred embodiments these compounds areacrylic and methacrylic esters such as methyl or ethyl acrylate, methylor ethyl methacrylate. When the selected alpha, beta-unsaturatedcompound comprises a compound of formula X wherein X' is oxygen, theresulting reaction product with the polyamine contains at least oneamido linkage (--C(O)N<) and such materials are herein termed"amido-amines." Similarly, when the selected alpha, beta unsaturatedcompound of formula X comprises a compound wherein X' is sulfur, theresulting reaction product with the polyamine contains thioamide linkage(--C(S)N<) and these materials are herein termed "thioamido-amines." Forconvenience, the following discussion is directed to the preparation anduse of amido-amines, although it will be understood that such discussionis also applicable to the thioamido-amines.

The type of amido-amine formed varies with reaction conditions. Forexample, a more linear amido-amine is formed where substantiallyequimolar amounts of the unsaturated carboxylate and polyamine arereacted. The presence of excesses of the ethylenically unsaturatedreactant of formula X tends to yield an amido-amine which is morecross-linked than that obtained where substantially equimolar amounts ofreactants are employed. Where for economic or other reasons across-linked amido-amine using excess amine is desired, generally amolar excess of the ethylenically unsaturated reactant of about at least10%, such as 10-300%, or greater, for example, 25-200%, is employed. Formore efficient cross-linking an excess of carboxylated material shouldpreferably be used since a cleaner reaction ensues. For example, a molarexcess of about 10-100% or greater such as 10-50%, but preferably anexcess of 30-50%, of the carboxylated material. Larger excess can beemployed if desired.

In summary, without considering other factors, equimolar amounts ofreactants tend to produce a more linear amido-amine whereas excess ofthe formula XII reactant tends to yield a more cross-linked amido-amine.It should be noted that the higher the polyamine (i.e., in greater thenumber of amino groups on the molecule) the greater the statisticalprobability of cross-linking since, for example, atetraalkylenepentamine, such as tetraethylene pentamine ##STR16## hasmore labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido andamino groups. In their simplest embodiments they may be represented byunits of the following idealized formula (XVIII): ##STR17## wherein theR¹⁰ 's, which may be the same or different, are hydrogen or asubstituted group, such as a hydrocarbon group, for example, alkyl,alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which,for example, may be aryl, cycloalkyl, alkyl, etc., and n₄ is an integersuch as 1-10 or greater.

The above simplified formula represents a linear amido-amine polymer.However, cross-linked polymers may also be formed by employing certainconditions since the polymer has labile hydrogens which can furtherreact with either the unsaturated moiety by adding across the doublebond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines employed in this invention are notcross-linked to any substantial degree, and more preferably aresubstantially linear.

Preferably, the polyamine reactant contains at least one primary amine(and more preferably from 2 to 4 primary amines) group per molecule, andthe polyamine and the unsaturated reactant of formula X are contacted inan amount of from about 1 to 10, more preferably from about 2 to 6, andmost preferably from about 3 to 5, equivalents of primary amine in thepolyamine reactant per mole of the unsaturated reactant of formula X.

The reaction between the selected polyamine and acrylate-type compoundis carried out at any suitable temperature. Temperatures up to thedecomposition points of reactants and products can be employed. Inpractice, one generally carries out the reaction by heating thereactants below 100° C., such as 80°-90° C., for a suitable period oftime, such as a few hours. Where an acrylic-type ester is employed, theprogress of the reaction can be judged by the removal of the alcohol informing the amide. During the early part of the reaction alcohol isremoved quite readily below 100° C. in the case of low boiling alcoholssuch as methanol or ethanol. As the reaction slows, the temperature israised to push the polymerization to completion and the temperature maybe raised to 150° C. toward the end of the reaction. Removal of alcoholis a convenient method of judging the progress and completion of thereaction which is generally continued until no more alcohol is evolved.Based on removal of alcohol, the yields are generally stoichiometric. Inmore difficult reactions, yield of at least 95% are generally obtained.

Similarly, it will be understood that the reaction of an ethylenicallyunsaturated carboxylate thioester of formula XII liberates thecorresponding HSR⁸ compound (e.g., H₂ S when R⁸ is hydrogen) as aby-product, and the reaction of an ethylenically unsaturatedcarboxyamide of formula XIII liberates the corresponding HNR⁸ (R⁹)compound (e.g., ammonia when R⁸ and R⁹ are each hydrogen) as by-product.

The reaction time involved can vary widely depending on a wide varietyof factors. For example, there is a relationship between time andtemperature. In general, lower temperature demands longer times.Usually, reaction times of from about 2 to 30 hours, such as 5 to 25hours, and preferably 3 to 10 hours will be employed.

Although one can employ a solvent, the reaction can be run without theuse of any solvent. In fact, where a high degree of cross-linking isdesired, it is preferably to avoid the use of a solvent and mostparticularly to avoid a polar solvent such as water. However, takinginto consideration the effect of solvent on the reaction, where desired,any suitable solvent can be employed, whether organic or inorganic,polar or non-polar.

As an example of the amido-amine adducts, the reaction of tetraethylenepentaamine (TEPA) with methyl methacrylate can be illustrated asfollows: ##STR18##

Preparation of the Dispersant

The halogenated ethylene alpha-olefin polymer and amine compound (e.g.,alkylene polyamine or polyalkylene polyamine) may be brought togetherneat or in the presence of an inert solvent, particularly a hydrocarbonsolvent. The inert hydrocarbon solvent may be aliphatic or aromatic.Also, aliphatic alcohols may be used by themselves or in combinationwith another solvent, when capable of dissolving the reactants.

The reaction may be carried out at room temperature (20° C.), butelevated temperatures are preferred. Usually, the temperature will be inthe range of from about 100° to 225° C. Depending on the temperature ofthe reaction, the particular halogen used, the mole ratios and theparticular amine, as well as the reactant concentrations, the time mayvary from 1 to 24 hours, more usually from about 3 to 20 hours. Timesgreatly in excess of 24 hours do not particularly enhance the yield andmay lead to undesirable degradation. It is therefore preferred to limitthe reaction time to fewer than 24 hours.

The mole ratio of halogenated ethylene alpha-olefin polymer to aminecompound will generally be in the range from about 0.2 to 10 moles ofamine compound per mole of halogenated ethylene alpha-olefin polymer,more usually 0.5 to 5 moles of amine compound per mole of halogenatedethylene alpha-olefin polymer. The mole ratio will depend upon theamount of halogen present in the halogenated ethylene alpha-olefinpolymer, the particular halogen and the desired ratio of polymer toamine compound.

Small amounts of residual halogen in the final composition are notdeleterious. Generally, the residual halogen, as bound halogen, will bein the range of 0 to 10 weight percent of the composition. Small amountsof halogen may be present as the hydrohalide salt of the polymersubstituted alkylene polyamines.

Since the ethylene alpha-olefin polymers used will have olefinicunsaturation, the amines may react in a way resulting in the eliminationof hydrogen halide, introducing further aliphatic unsaturation into thepolymer radical. However, the olefinic unsaturation does notsignificantly affect the utility of the product, and when available,saturated aliphatic halide may be used.

After the reaction has been carried out for a sufficient length of time,the reaction mixture may be extracted with a hydrocarbon medium to freethe product from any low molecular weight amine salt which has formed.The product may then be isolated by evaporation of the solvent. Furtherseparation from unreacted polymer or purification may be carried out asdesired, e.g., chromatography.

An example of the reaction of an amido-amine reactant with a halogenatedpolymer is the reaction of chlorinated ethylene-propylene copolymer(EP-Cl) with a polyamido-amine having two terminal --NH₂ groups, whichcan be illustrated as follows: ##STR19## wherein x and y are eachintegers of from 0 to 10, EP represents an ethylene-propylene copolymergroup as described above, Z¹ and Z² are moieties of the formula:##STR20## wherein R¹⁰, A and n₄ are as defined above for Formula XVIII.Preferred are amido-amine reaction products of the above equationwherein R¹⁰ is H, and most preferably wherein x and y are each zero, andA is --(CH₂)₂ -- or --(CH₃ H₇)--.

It will be understood that the amine reactant can comprise one or amixture of any of the above described amines, such as a mixture of anamido-amine and a polyalkylene polyamine. Preferably, the halogenatedpolymer and amine will be contacted for a time and under conditionssufficient to react substantially all of the primary nitrogens in theamine reactant. The progress of this reaction can be followed byinfrared analysis.

The dispersant-forming reaction can be conducted in a polar or non-polarsolvent (e.g., xylene, toluene, benzene and the like), and is preferablyconducted in the presence of a mineral or synthetic lubricating oil.

Hydroxyamines which can be reacted with the aforesaid ethylenealpha-olefin polymer substituted dicarboxylic acid material to formdispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propane-diol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N'-(beta-amino-ethyl)-piperazine,tris(hydroxymethyl) amino-methane (also known astrismethylolaminomethane) 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)-ethylamine, and the like. Mixtures of these orsimilar amines can also be employed. The above description ofnucleophilic reactants suitable for reaction with the ethylenealpha-olefin polymer substituted dicarboxylic acid or anhydride includesamines, alcohols, and compounds of mixed amine and hydroxy containingreactive functional groups, i.e., amino-alcohols.

A preferred group of ashless dispersants are those derived fromchlorinated ethylene-propylene copolymer and reacted with polyethyleneamines (referred to herein as "EPSA"), e.g., ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene pentamine,pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines,e.g., polyoxypropylene diamine, trismethylolaminomethane andpentaerythritol, and combinations thereof.

The dispersant materials of this invention are preferably characterizedby a VR' value of not greater than about 4.1, preferably not greaterthan about 4.0, e.g., from about 2.5 to 4.0, and most preferably fromabout 3.5 to 3.9. As used herein, the term "VR' value" is intended torefer to the quotient obtained by the expression (XIX): ##EQU2## whereinVIS'a is the kinematic viscosity (ASTM Method D445) of the dispersantmaterial at 100° C. in units of centistokes, and VIS'b is the coldcranking simulator (CCS) viscosity (ASTM Method D2602) at -20° C. inunits of poise, as determined at a dispersant material polymerconcentration of 2 wt.% in the reference oil as defined above forFormula IV. Preferably, the disperant materials of this invention arealso characterized by a VR'/VR_(r) ratio of not greater than about 1.11,more preferably not greater than about 1.09, still more preferably fromabout 0.7 to 1.08 and most preferably from about 0.9 to 1.05, whereinVR_(r) =3.7±0.1 for the reference oil.

Another aspect of this invention involves the post treatment of thenitrogen containing dispersant materials. The process for post-treatingsaid nitrogen containing dispersant materials is analogous to thepost-treating processes used with respect to derivatives of conventionalethylene copolymers of the prior art. Accordingly, the same reactionconditions, ratio of reactants and the like can be used.

The nitrogen-containing dispersant materials of the instant invention asdescribed above are post-treated by contacting said nitrogen-containingdispersant materials with one or more post-treating reagents selectedfrom the group consisting of boron oxide, boron oxide hydrate, boronhalides, boron acids, esters of boron acids, carbon disulfide, sulfur,sulfur chlorides, alkenyl cyanides, aldehydes, ketones, urea, thio-urea,guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbylphosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphites, C₁to C₃₀ hydrocarbyl substituted succinic acids and anhydrides (e.g.,succinic anhydride, dodecyl succinic anhydride and the like), maleicanhydride (or any of the above discussed monounsaturated carboxylicreactants useful in forming the ethylene-alpha-olefinpolymer-substituted mono- and dicarboxylic acid materials employed inthis invention), phosphorus sulfides, phosphorus oxides, phosphoricacid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbylisothiocyantes, epoxides, episulfides, formaldehyde orformaldehyde-producing compounds plus phenols, and sulfur plus phenols.

For example, the nitrogen containing dispersants can be treated with aboron compound selected from the class consisting of boron oxide, boronhalides, boron acids and esters of boron acids in an amount to providefrom about 0.1 atomic proportion of boron for each mole of said nitrogencomposition to about 20 atomic proportions of boron for each atomicproportion of nitrogen of said nitrogen composition. Usefully theborated dispersants of the invention contain from about 0.05 to 2.0wt.%, e.g., 0.05 to 0.7 wt.% boron based on the total weight of saidborated nitrogen-containing dispersant compound. The boron, whichappears to be in the product as dehydrated boric acid polymers(primarily (HBO₂)₃), is believed to attach to the dispersant as aminesalts, e.g., the metaborate salt of said amine dispersants.

Treating is readily carried out by adding from about 0.05 to 4, e.g. 1to 3 wt.% (based on the weight of said nitrogen compound) of said boroncompound, preferably boric acid which is most usually added as a slurryto said nitrogen compound and heating with stirring at from about 135°C. to 190, e.g., 140°-170° C., for from 1 to 5 hours followed bynitrogen stripping at said temperature ranges. Or, the boron treatmentcan be carried out by adding boric acid to the hot reaction mixture ofthe dicarboxylic acid material and amine while removing water.

Since post-treating processes involving the use of these post-treatingreagents is known insofar as application to reaction products of aminesand halogenated polymers, further descriptions of these processes hereinis unnecessary. In order to apply the prior art processes to thecompositions of this invention, all that is necessary is that reactionconditions, ratio of reactants, and the like as described in the priorart, be applied to the novel compositions of this invention. Thefollowing U.S. patents are expressly incorporated herein by referencefor their disclosure of post-treating processes and post-treatingreagents applicable to the compositions of this invention: U.S. Pat.Nos. 3,087,936; 3,200,107; 3,254,025; 3,256,185; 3,278,550; 3,281,428;3,282,955; 3,284,410; 3,338,832, 3,344,069; 3,366,569; 3,373,111;3,367,943; 3,390,086; 3,403,102; 3,428,561; 3,470,098; 3,502,677;3,513,093; 3,533,945; 3,541,012; 3,639,242; 3,708,522; 3,859,318;3,865,813; 3,470,098; 3,369,021; 3,184,411; 3,185,645; 3,245,908;3,245,909; 3,245,910; 3,558,743; 3,573,205; 3,692,681; 3,749,695;3,865,740; 3,954,639; 3,458,530; 3,390,086; 3,367,943; 3,185,704,3,551,466; 3,415,750; 3,312,619; 3,280,034; 3,718,663; 3,652,616;4,338,205; 4,428,849; 4,686,054; 4,839,070; 4,839,071; 4,839,072;4,839,073; U.K. Pat. No. 1,085,903; U.K. Pat. No. 1,162,436.

The nitrogen containing dispersant materials of this invention can alsobe treated with polymerizable lactones (such as epsilon-caprolactone) toform dispersant adducts having the moiety --[C(O)(CH₂)_(z) O]_(m) H,wherein z is a number of from 4 to 8 (e.g., 5 to 7) and m has an averagevalue of from about 0 to 100 (e.g., 0.2 to 20). The dispersants of thisinvention can be post-treated with a C₅ to C9 lactone, e.g.,epsilon-caprolactone, by heating a mixture of the dispersant materialand lactone in a reaction vessel in the absence of a solvent at atemperature of about 50° C. to about 200° C., more preferably from about75° C. to about 180° C., and most preferably from about 90° C. to about160 C., for a sufficient period of time to effect reaction. Optionally,a solvent for the lactone, dispersant material and/or the resultingadduct may be employed to control viscosity and/or the reaction rates.

In one p referred embodiment, the C₅ to C9 lactone, e.g.,epsilon-caprolactone, is reacted with a dispersant material in a 1:1mole ratio of lactone to dispersant material. In practice, the ration oflactone to dispersant material may vary considerably as a means ofcontrolling the length of the sequence of the lactone units in theadduct. For example, the mole ratio of the lactone to the dispersantmaterial may vary from about 10:1 to about 0.1:1, more preferably fromabout 5:1 to about 0.2:1, and most preferably from about 2:1 to about0.4:1. It is preferable to maintain the average degree of polymerizationof the lactone monomer below about 100, with a degree of polymerizationon the order of from about 0.2 to about 50 being preferred, and fromabout 0.2 to about 20 being more preferred. For optimum dispersantperformance, sequences of from about 1 to about 5 lactone units in a roware preferred.

Catalysts useful in the promotion of the lactone-dispersant materialreactions are selected from the group consisting of stannous octanoate,stannous hexanoate, tetrabutyl titanate, a variety of organic based acidcatalysts and amine catalysts, as described on page 266, and forward, ina book chapter authored by R.D. Lundberg and E. F. Cox, entitled"Kinetics and Mechanisms of Polymerization: Ring OpeningPolymerization", edited by Frisch and Reegen, published by Marcel Dekkerin 1969, wherein stannous octanoate is an especially preferred catalyst.The catalyst is added to the reaction mixture at a concentration levelof about 50 to about 10,000 parts per weight of catalyst per one millionparts of the total reaction mixture.

Exemplary of adducts formed by reaction of dispersant materials if thisinvention and epsiloncaprolactone are those adducts illustrated by thefollowing equation: ##STR21## wherein m and EP are as defined above. Thereactions of such lactones with dispersant materials containing nitrogenor ester groups is more completely described in U.S. Pat. Nos.4,486,326; 4,820,432; 4,828,742; 4,851,524; 4,866,135; 4,866,139;4,866,140; 4,866,141; 4,866,142; and 4,866,187, the disclosure of eachof which is hereby incorporated by reference in its entirety.

Further aspects of the present invention reside in the formation ofmetal complexes of the novel dispersant additives prepared in accordancewith this invention. Suitable metal complexes may be formed inaccordance with known techniques of employing a reactive metal ionspecies during or after the formation of the present dispersantmaterials. Complex forming metal reactants include the metal nitrates,thiocyanates, halides, carboxylates, phosphates, thio-phosphates,sulfates, and borates of transition metals such as iron, cobalt, nickel,copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium,platinum, cadmium, lead, silver, mercury, antimony and the like. Priorart disclosures of these complexing reactions may be also found in U.S.Pat. Nos. 3,306,908 and Re. 26,433, the disclosures of which are herebyincorporated by reference in their entirety.

The processes of these incorporated patents, as applied to thecompositions of this invention, and the post-treated compositions thusproduced constitute a further aspect of this invention.

As a further feature of the present invention, the (A) halogenatedethylene-alpha-olefin polymers of this invention can be admixed, priorto, after or during being contacted with the selected amine(s), with (B)a conventional halogenated polyolefin derived from any of thepolyolefins discussed above as being useful as a mixed charge with thehalogenated ethylene-alpha-olefin polymers in the formation of thehalogenated ethylene-alpha-olefin polymers of this invention. Thehalogenated ethylene-alpha-olefin polymers of this invention and thehalogenated polyolefins will be generally admixed prior to contact withthe selected amine(s), e.g., alkylene polyamine. Such mixtures willgenerally employ a weight:weight ratio of halogenatedethylene-alpha-olefin polymers of this invention to halogenatedpolyolefin from about 10:90 to 90:10, preferably from about 20:80 to80:20, and more preferably from about 40:60 to 60:40. Especiallypreferred are mixtures of halogenated ethylene-propylene copolymers ofthis invention and halogenated polyisobutylene, halogenatedpoly-n-butene, or mixtures thereof, having a number average molecularweight as described above for the above conventional polyolefins, (e.g.,900-5,000). The resulting mixtures can then be contacted for reactionwith the selected amine as described above for formation of dispersantmaterials having improved viscosity properties, wherein the VR' of theresulting dispersant material is preferably less than the VR' of thecorresponding dispersant prepared from the polyolefin-substituted mono-or dicarboxylic acid material alone. The resulting mixed dispersantmaterials can also be treated with any of the above-describedpost-treatment methods for incorporation of additional functional groupsthereon, such as boron, hydroxy, ester, epoxy, lactone, sulfur, metalsand the like, as discussed above.

The dispersants of the present invention can be incorporated into alubricating oil (or a fuel) in any convenient way. Thus, these mixturescan be added directly to the lubricating oil (or fuel) by dispersing ordissolving the same in the lubricating oil (or fuel) at the desiredlevel of concentration of the dispersant. Such blending into theadditional lubricating oil (or fuel) can occur at room temperature orelevated temperatures. Alternatively, the dispersants can be blendedwith a suitable oil-soluble solvent/diluent (such as benzene, xylene,toluene, lubricating base oils and petroleum distillates, including thevarious normally liquid fuels described in detail below) to form aconcentrate, and then blending the concentrate with a lubricating oil(or fuel) to obtain the final formulation. Such dispersant concentrateswill typically contain (on an active ingredient (A.I.) basis) from about3 to about 45 wt.%, and preferably from about 10 to about 35 wt.%,dispersant additive, and typically from about 30 to 90 wt.%, preferablyfrom about 40 to 60 wt.%, base oil, based on the concentrate weight.

OLEAGINOUS COMPOSITIONS

The additive mixtures of the present invention possess very gooddispersant properties as measured herein in a wide variety ofenvironments. Accordingly, the additive mixtures are used byincorporation and dissolution into an oleaginous material such as fuelsand lubricating oils. When the additive mixtures of this invention areused in normally liquid petroleum fuels such as middle distillatesboiling from about 65° to 430° C., including kerosene, diesel fuels,home heating fuel oil, jet fuels, etc., a concentration of the additivesin the fuel in the range of typically from about 0.001 to about 0.5, andpreferably 0.005 to about 0.15 weight percent, based on the total weightof the composition, will usually be employed. The properties of suchfuels are well known as illustrated, for example, by ASTM SpecificationsD #396-73 (Fuel Oils) and D #439-73 (Gasolines) available from theAmerican Society for Testing Materials ("ASTM"), 1916 Race Street,Philadelphia, Penna. 19103.

The fuel compositions of this invention can contain, in addition to theproducts of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes, depositpreventers or modifiers such as triaryl phosphates, dyes, cetaneimprovers, anitoxidants such as 2,6-ditertiary-butyl-4-methylphenol,rust inhibitors, bacteriostatic agents, gum inhibitors, metaldeactivators, upper cylinder lubricants and the like.

The products of the present invention find their primary utility inlubricating oil compositions which employ a base oil in which theadditives re dissolved or dispersed. Such base oils may be natural orsynthetic. Base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additivemixtures of the present invention in base oils conventionally employedin and/or adapted for use as power transmitting fluids, universaltractor fluids and hydraulic fluids, heavy duty hydraulic fluids, powersteering fluids and the like. Gear lubricants, industrial oils, pumpoils and other lubricating oil compositions can also benefit from theincorporation therein of the additive mixtures of the present invention.

These lubricating oil formulations conventionally contain severaldifferent types of additives that will supply the characteristics thatare required in the formulations. Among these types of additives areincluded viscosity index improvers, antioxidants, corrosion inhibitors,detergents, dispersants, pour point depressants, antiwear agents,friction modifiers, and other ashless dispersant (e.g., polyisobutenylsuccinimides) and borated derivatives thereof), etc.

In the preparation of lubricating oil formulations it is common practiceto introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80wt. % active ingredient concentrates in hydrocarbon oil, e.g. minerallubricating oil, or other suitable solvent. Usually these concentratesmay be diluted with 3 to 100, e.g., 5 to 40 parts by weight oflubricating oil, per part by weight of the additive package, in formingfinished lubricants, e.g. crankcase motor oils. The purpose ofconcentrates, of course, is to make the handling of the variousmaterials less difficult and awkward as well as to facilitate solutionor dispersion in the final blend. Thus, a dispersant would be usuallyemployed in the form of a 40 to 50 wt. % concentrate, for example, in alubricating oil fraction.

The ashless dispersants of the present invention will be generally usedin admixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methyl-poly isopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of poly-ethylene glycol having a molecularweight of 500-1000, diethyl ether of polypropylene glycol having amolecular weight of 1000-1500) ; and mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃ -C₈ fatty acidesters and C₁₃ Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting one moleof sebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tert-butylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane,poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other syntheticlubricating oils include liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester ofdecylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Metal containing rust inhibitors and/or detergents are frequently usedwith ashless dispersants. Such detergents and rust inhibitors includethe metal salts of sulphonic acids, alkyl phenols, sulphurized alkylphenols, alkyl salicylates, naphthenates, and other oil soluble mono-and di-carboxylic acids. Highly basic, that is overbased metal saltswhich are frequently used as detergents appear particularly prone tointeraction with the ashless dispersant. Usually these metal containingrust inhibitors and detergents are used in lubricating oil in amounts ofabout 0.01 to 10, e.g. 0.1 to 5 wt. %, based on the weight of the totallubricating composition. Marine diesel lubricating oils typically employsuch metal-containing rust inhibitors and detergents in amounts of up toabout 20 wt.%.

Highly basic alkaline earth metal sulfonates are frequently used asdetergents. They are usually produced by heating a mixture comprising anoil-soluble sulfonate or alkaryl sulfonic acid, with an excess ofalkaline earth metal compound above that required for completeneutralization of any sulfonic acid present and thereafter forming adispersed carbonate complex by reacting the excess metal with carbondioxide to provide the desired overbasing. The sulfonic acids aretypically obtained by the sulfonation of alkyl substituted aromatichydrocarbons such as those obtained from the fractionation of petroleumby distillation and/or extraction or by the alkylation of aromatichydrocarbons as for example those obtained by alkylating benzene,toluene, xylene, naphthalene, diphenyl and the halogen derivatives suchas chlorobenzene, chlorotoluene and chloronaphthalene. The alkylationmay be carried out in the presence of a catalyst with alkylating agentshaving from about 3 to more than 30 carbon atoms. For examplehaloparaffins, olefins obtained by dehydrogenation of paraffins,polyolefins produced from ethylene, propylene, etc. are all suitable.The alkaryl sulfonates usually contain from about 9 to about 70 or morecarbon atoms, preferably from about 16 to about 50 carbon atoms peralkyl substituted aromatic moiety.

The alkaline earth metal compounds which may be used in neutralizingthese alkaryl sulfonic acids to provide the sulfonates includes theoxides and hydroxides, alkoxides, carbonates, carboxylate, sulfide,hydrosulfide, nitrate, borates and ethers of magnesium, calcium, andbarium. Examples are calcium oxide, calcium hydroxide, magnesium acetateand magnesium borate. As noted, the alkaline earth metal compound isused in excess of that required to complete neutralization of thealkaryl sulfonic acids. Generally, the amount ranges from about 100 to220%, although it is preferred to use at least 125%, of thestoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkaline earth metal alkarylsulfonates are known, such as U.S. Pat. Nos. 3,150,088 and 3,150,089wherein overbasing is accomplished by hydrolysis of analkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbonsolvent-diluent oil.

A preferred alkaline earth sulfonate additive is magnesium alkylaromatic sulfonate having a total base number ranging from about 300 toabout 400 with the magnesium sulfonate content ranging from about 25 toabout 32 wt. %, based upon the total weight of the additive systemdispersed in mineral lubricating oil.

Neutral metal sulfonates are frequently used as rust inhibitors.Polyvalent metal alkyl salicylate and naphthenate materials are knownadditives for lubricating oil compositions to improve their hightemperature performance and to counteract deposition of carbonaceousmatter on pistons (U.S. Pat. No. 2,744,069). An increase in reservebasicity of the polyvalent metal alkyl salicylates and naphthenates canbe realized by utilizing alkaline earth metal, e.g. calcium, salts ofmixtures of C₈ -C₂₆ alkyl salicylates and phenates (see U.S. Pat. No.2,744,069) or polyvalent metal salts of alkyl salicyclic acids, saidacids obtained from the alkylation of phenols followed by phenation,carboxylation and hydrolysis (U.S. Pat. No. 3,704,315) which could thenbe converted into highly basic salts by techniques generally known andused for such conversion. The reserve basicity of these metal-containingrust inhibitors is usefully at TBN levels of between about 60 and 150.Included with the useful polyvalent metal salicylate and naphthenatematerials are the methylene and sulfur bridged materials which arereadily derived from alkyl substituted salicylic or naphthenic acids ormixtures of either or both with alkyl substituted phenols. Basicsulfurized salicylates and a method for their preparation is shown inU.S. Pat. No. 3,595,791. Such materials include alkaline earth metal,particularly magnesium, calcium, strontium and barium salts of aromaticacids having th general formula:

    HOOC--ArR.sub.1 --Xy(ArR.sub.1 OH)n                        (XX)

where Ar is an aryl radical of 1 to 6 rings, R₁ is an alkyl group havingfrom about 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms(optimally about 12), X is a sulfur (--S--) or methylene (--CH₂ --)bridge, y is a number from 0 to 4 and n is a number from 0 to 4.

Preparation of the overbased methylene bridged salicylate-phenate saltis readily carried out by conventional techniques such as by alkylationof a phenol followed by phenation, carboxylation, hydrolysis, methylenebridging a coupling agent such as an alkylene dihalide followed by saltformation concurrent with carbonation. An overbased calcium salt o f amethylene bridged phenol-salicylic acid of the general formula (XXI):##STR22## with a TBN of 60 to 150 is highly useful in this invention.

The sulfurized metal phenates can be considered the "metal salt of aphenol sulfide" which thus refers to a metal salt whether neutral orbasic, of a compound typified by the general formula (XXII): ##STR23##where x=1 or 2, n=0, 1 or 2; or a polymeric form of such a compound,where R is an alkyl radical, n and x are each integers from 1 to 4, andthe average number of carbon atoms in all of the R groups is at leastabout 9 in order to ensure adequate solubility in oil. The individual Rgroups may each contain from 5 to 40, preferably 8 to 20, carbon atoms.The metal salt is prepared by reacting an alkyl phenol sulfide with asufficient quantity of metal containing material to impart the desiredalkalinity to the sulfurized metal phenate.

Regardless of the manner in which they are prepared, the sulfurizedalkyl phenols which are useful generally contain from about 2 to about14% by weight, preferably about 4 to about 12 wt. % sulfur based on theweight of sulfurized alkyl phenol.

The sulfurized alkyl phenol may be converted by reaction with a metalcontaining material including oxides, hydroxides and complexes in anamount sufficient to neutralize said phenol and, if desired, to overbasethe product to a desired alkalinity by procedures well known in the art.Preferred is a process of neutralization utilizing a solution of metalin a glycol ether.

The neutral or normal sulfurized metal phenates are those in which theratio of metal to phenol nucleus is about 1:2. The "overbased" or"basic" sulfurized metal phenates are sulfurized metal phenates whereinthe ratio of metal to phenol is greater than that of stoichiometric,e.g. basic sulfurized metal dodecyl phenate has a metal content up toand greater than 100% in excess of the metal present in thecorresponding normal sulfurized metal phenates wherein the excess metalis produced in oil-soluble or dispersible form (as by reaction withCO₂). The overbased sulfurized metal phenates desirably have a TBN valueof at least 150, e.g. from 200 to 300.

Magnesium and calcium containing additives although beneficial in otherrespects can increase the tendency of the lubricating oil to oxidize.This is especially true of the highly basic sulphonates.

According to a preferred embodiment the invention therefore provides acrankcase lubricating composition also containing from 2 to 8000 partsper million of calcium or magnesium.

The magnesium and/or calcium is generally present as basic or neutraldetergents such as the sulphonates and phenates, our preferred additivesare the neutral or basic magnesium or calcium sulphonates. Preferablythe oils contain from 500 to 5000 parts per million of calcium ormagnesium. Basic magnesium and calcium sulphonates are preferred.

A particular advantage of the novel dispersants of the present inventionis use with V.I improvers to form multi-grade automobile enginelubricating oils. Viscosity modifiers impart high and low temperatureoperability to the lubricating oil and permit it to remain relativelyviscous at elevated temperatures and also exhibit acceptable viscosityor fluidity at low temperatures. Viscosity modifiers are generally highmolecular weight hydrocarbon polymers including polyesters. Theviscosity modifiers may also be derivatized to include other propertiesor functions, such as the addition of dispersancy properties. These oilsoluble viscosity modifying polymers will generally have number averagemolecular weights of from 10³ to 10⁶, preferably 10⁴ to 10⁶, e.g.,20,000 to 250,000, as determined by gel permeation chromatography orosmometry.

Examples of suitable hydrocarbon polymers include homopolymers andcopolymers of two or more monomers of C₂ to C₃₀, e.g. C₂ to C₈ olefins,including both alpha olefins and internal olefins, which may be straightor branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.Frequently they will be of ethylene with C₃ to C₃₀ olefins, particularlypreferred being the copolymers of ethylene and propylene. Other polymerscan be used such as polyisobutylenes, homopolymers and copolymers of C₆and higher alpha olefins, atactic polypropylene, hydrogenated polymersand copolymers and terpolymers of styrene, e.g., with isoprene and/orbutadiene and hydrogenated derivatives thereof. The polymer may bedegraded in molecular weight, for example by mastication, extrusion,oxidation or thermal degradation, and it may be oxidized and containoxygen. Also included are derivatized polymers such as post-graftedinterpolymers of ethylene-propylene with an active monomer such asmaleic anhydride which may be further reacted with an alcohol, or amine,e.g. an alkylene polyamine or hydroxy amine, e.g. see U.S. Pat. Nos.4,089,794; 4,160,739; 4,137,185; or copolymers of ethylene and propylenereacted or grafted with nitrogen compounds such as shown in U.S. Pat.Nos. 4,068,056; 4,068,058; 4,146,489 and 4,149,984.

The preferred hydrocarbon polymers are ethylene copolymers containingfrom 15 to 90 wt.% ethylene, preferably 30 to 80 wt.% of ethylene and 10to 85 wt.%, preferably 20 to 70 wt.% of one or more C₃ to C₂₈,preferably C₃ to C₁₈, more preferably C₃ to C₈, alpha-olefins. While notessential, such copolymers preferably have a degree of crystallinity ofless than 25 wt.%, as determined by X-ray and differential scanningcalorimetry. Copolymers of ethylene and propylene are most preferred.Other alpha-olefins suitable in place of propylene to form thecopolymer, or to be used in combination with ethylene and propylene, toform a terpolymer, tetrapolymer, etc., include 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branchedchain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene,5-methylpentene-1 , 4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc.,and mixtures thereof.

Terpolymers, tetrapolymers, etc., of ethylene, said C₃₋₂₈ alpha-olefin,and a non-conjugated diolefin or mixtures of such diolefins may also beused. The amount of the non-conjugated diolefin generally ranges fromabout 0.5 to 20 mole percent, preferably from about 1 to about 7 molepercent, based on the total amount of ethylene and alpha-olefin present.

The polyester V.I. improvers are generally polymers of esters ofethylenically unsaturated C₃ to C₈ mono- and dicarboxylic acids such asmethacrylic and acrylic acids, maleic acid, maleic anhydride, fumaricacid, etc.

Examples of unsaturated esters that may be used include those ofaliphatic saturated mono alcohols of at least 1 carbon atom andpreferably of from 12 to 20 carbon atoms, such as decyl acrylate, laurylacrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate,decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetylmethacrylate, stearyl methacrylate, and the like and mixtures thereof.

Other esters include the vinyl alcohol esters of C₂ to C₂₂ fatty or monocarboxylic acids, preferably saturated such as vinyl acetate, vinyllaurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like andmixtures thereof. Copolymers of vinyl alcohol esters with unsaturatedacid esters such as the copolymer of vinyl acetate with dialkylfumarates, can also be used.

The esters may be copolymerized with still other unsaturated monomerssuch as olefins, e.g. 0.2 to 5 moles of C₂ -C₂₀ aliphatic or aromaticolefin per mole of unsaturated ester, or per mole of unsaturated acid oranhydride followed by esterification. For example, copolymers of styrenewith maleic anhydride esterified with alcohols and amines are known,e.g., see U.S. Pat. No. 3,702,300.

Such ester polymers may be grafted with, or the ester copolymerizedwith, polymerizable unsaturated nitrogen-containing monomers to impartdispersancy to the V.I. improvers. Examples of suitable unsaturatednitrogen-containing monomers include those containing 4 to 20 carbonatoms such as amino substituted olefins asp-(beta-diethylaminoethyl)styrene; basic nitrogen-containingheterocycles carrying a polymerizable ethylenically unsaturatedsubstituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines suchas 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine,2-vinyl-pyridine, 4-vinylpyridine, 3-vinyl-pyridine,3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine,4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like.

N-vinyl lactams are also suitable, e.g., N-vinyl pyrrolidones or N-vinylpiperidones.

The vinyl pyrrolidones are preferred and are exemplified by N-vinylpyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, etc.

Dihydrocarbyl dithiophosphate metal salts are frequently used asanti-wear agents and also provide antioxidant activity. The zinc saltsare most commonly used in lubricating oil in amounts of 0.1 to 10,preferably 0.2 to 2 wt.%, based upon the total weight of the lubricatingoil composition. They may be prepared in accordance with knowntechniques by first forming a dithiophosphoric acid, usually by reactionof an alcohol or a phenol with P₂ S₅ and then neutralizing thedithiophosphoric acid with a suitable zinc compound.

Mixtures of alcohols may be used including mixtures of primary andsecondary alcohols, secondary generally for imparting improved anti-wearproperties, with primary giving improved thermal stability properties.Mixtures of the two are particularly useful. In general, any basic orneutral zinc compound could be used but the oxides, hydroxides andcarbonates are most generally employed. Commercial additives frequentlycontain an excess of zinc due to use of an excess of the basic zinccompound in the neutralization reaction.

The zinc dihydrocarbyl dithiophosphates useful in the present inventionare oil soluble salts of dihydrocarbyl esters of dithiophosphoric acidsand may be represented by the following formula: ##STR24## wherein R andR' may be the same or different hydrocarbyl radicals containing from 1to 18, preferably 2 to 12 carbon atoms and including radicals such asalkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals.Particularly preferred as R and R' groups are alkyl groups of 2 to 8carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl,i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl,decyl, dodecyl, octadecyl, 2-ethylhex yl, phenyl, butylphenyl,cyclohexyl, methylcyclopentyl, propenyl, butenyl etc. In order to obtainoil solubility, the total number of carbon atoms (i.e., R and R' informula XXIII) in the dithiophosphoric acid will generally be about 5 orgreater.

The antioxidants useful in this invention include oil soluble coppercompounds. The copper may be blended into the oil as any suitable oilsoluble copper compound. By oil soluble we mean the compound is oilsoluble under normal blending conditions in the oil or additive package.The copper compound may be in the cuprous or cupric form. The copper maybe in the form of the copper dihydrocarbyl thio- or dithio-phosphateswherein copper may be substituted for zinc in the compounds andreactions described above although one mole of cuprous or cupric oxidemay be reacted with one or two moles of the dithiophosphoric acid,respectively. Alternatively the copper may be added as the copper saltof a synthetic or natural carboxylic acid. Examples include C₁₀ to C₁₈fatty acids such as stearic or palmitic, but unsaturated acids such asoleic or branched carboxylic acids such as napthenic acids of molecularweight from 200 to 500 or synthetic carboxylic acids are preferredbecause of the improved handling and solubility properties of theresulting copper carboxylates. Also useful are oil soluble copperdithiocarbamates of the general formula (RR'NCSS)_(n) Cu, where n is 1or 2 and R and R' are the same or different hydrocarbyl radicalscontaining from 1 to 18 and preferably 2 to 12 carbon atoms andincluding radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl andcycloaliphatic radicals. Particularly preferred as R and R' groups arealkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, forexample, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl,2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl,propenyl, butenyl, etc. In order to obtain oil solubility, the totalnumber of carbon atoms (i.e., R and R') will generally be about 5 orgreater. Copper sulphonates, phenates, and acetylacetonates may also beused.

Exemplary of useful copper compounds are copper (Cu^(I) and/or Cu^(II))salts of alkenyl succinic acids or anhydrides. The salts themselves maybe basic, neutral or acidic. They may be formed by reacting (a) any ofthe ashless dispersants discussed above, which have at least one freecarboxylic acid (or anhydride) group with (b) a reactive metal compound.Suitable acid (or anhydride) reactive metal compounds include those suchas cupric or cuprous hydroxides, oxides, acetates, borates, andcarbonates or basic copper carbonate.

Examples of the metal salts of this invention are Cu salts ofpolyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA),and Cu salts of polyisobutenyl succinic acid. Preferably, the selectedmetal employed is its divalent form, e.g., Cu⁺². The preferredsubstrates are polyalkenyl succinic acids in which the alkenyl group hasa molecular weight greater than about 700. The alkenyl group desirablyhas a M_(n) from about 900 to 1400, and up to 2500, with a M_(n) ofabout 950 being most preferred. Especially preferred is polyisobutylenesuccinic acid (PIBSA). These materials may desirably be dissolved in asolvent, such as a mineral oil, and heated in the presence of a watersolution (or slurry) of the metal bearing material. Heating may takeplace between 70° and about 200° C. Temperatures of 110° to 140° C. areentirely adequate. It may be necessary, depending upon the saltproduced, not to allow the reaction to remain at a temperature aboveabout 140° C. for an extended period of time, e.g., longer than 5 hours,or decomposition of the salt may occur.

The copper antioxidants (e.g., Cu-PIBSA, Cu-oleate, or mixtures thereof)will be generally employed in an amount of from about 50-500 ppm byweight of the metal, in the final lubricating composition.

The copper antioxidants used in this invention are inexpensive and areeffective at low concentrations and therefore do not add substantiallyto the cost of the product. The results obtained are frequently betterthan those obtained with previously used antioxidants, which areexpensive and used in higher concentrations. In the amounts employed,the copper compounds do not interfere with the performance of othercomponents of the lubricating composition, in many instances, completelysatisfactory results are obtained when the copper compound is the soleantioxidant in addition to the ZDDP. The copper compounds can beutilized to replace part or all of the need for supplementaryantioxidants. Thus, for particularly severe conditions it may bedesirable to include a supplementary, conventional antioxidant. However,the amounts of supplementary antioxidant required are small, far lessthan the amount required in the absence of the copper compound.

While any effective amount of the copper antioxidant can be incorporatedinto the lubricating oil composition, it is contemplated that sucheffective amounts be sufficient to provide said lube oil compositionwith an amount of the copper antioxidant of from about 5 to 500 (morepreferably 10 to 200, still more preferably 10 to 180, and mostpreferably 20 to 130 (e.g., 90 to 120)) part per million of added copperbased on the weight of the lubricating oil composition. Of course, thepreferred amount may depend amongst other factors on the quality of thebasestock lubricating oil.

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are phosphosulfurizedhydrocarbons and the products obtained by reaction of aphosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, preferably in the presence of an alkylated phenol or of analkylphenol thioester, and also preferably in the presence of carbondioxide. Phosphosulfurized hydrocarbons are prepared by reacting asuitable hydrocarbon such as a terpene, a heavy petroleum fraction of aC₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30weight percent of a sulfide of phosphorus for 1/2 to 15 hours, at atemperature in the range of 65 to 315° C. Neutralization of thephosphosulfurized hydrocarbon may be effected in the manner taught inU.S. Pat. No. 1,969,324.

Oxidation inhibitors reduce the tendency of mineral oils to deterioratein service which deterioration can be evidenced by the products ofoxidation such as sludge and varnish-like deposits on the metal surfacesand by viscosity growth. Such oxidation inhibitors include alkalineearth metal salts of alkylphenolthioesters having preferably C₅ to C₁₂alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenylsulfide, dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurizedor sulfurized hydrocarbons, etc.

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable friction modifiers are found in U.S.Pat. No. 3,933,659 which discloses fatty acid esters and amides; U.S.Pat. No. 4,176,074 which describes molybdenum complexes ofpolyisobutenyl succinic anhydride-amino alkanols; U.S. Pat. No.4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.Pat. No. 3,779,928 which discloses alkane phosphonic acid salts; U.S.Pat. No. 3,778,375 which discloses reaction products of a phosphonatewith an oleamide; U.S. Pat. No. 3,852,205 which disclosesS-carboxy-alkylene hydrocarbyl succinimide, S-carboxyalkylenehydrocarbyl succinamic acid and mixtures thereof; U.S. Pat. No.3,879,306 which discloses N-(hydroxyalkyl) alkenyl-succinamic acids orsuccinimides; U.S. Pat. No. 3,932,290 which discloses reaction productsof di-(lower alkyl) phosphites and epoxides; and U.S. Pat. No. 4,028,258which discloses the alkylene oxide adduct of phosphosulfurizedN-(hydroxyalkyl) alkenyl succinimides. The disclosures of the abovereferences are herein incorporated by reference. The most preferredfriction modifiers are glycerol mono and dioleates, and succinateesters, or metal salts thereof, of hydrocarbyl substituted succinicacids or anhydrides and thiobis alkanols such as described in U.S. Pat.No. 4,344,853.

Pour point depressants lower the temperature at which the lubricatingoil will flow or can be poured. Such depressants are well known. Typicalof those additives which usefully optimize the low temperature fluidityof the flui d a re C₈ -C₁₈ dia lkylfumarate vinyl acetate copolymers,polymethacrylates, and wax naphthalene.

Foam control can be provided by an antifoamant of the polysiloxane type,e.g. silicone oil and polydimethyl siloxane.

Organic, oil-soluble compounds useful as rust inhibitors in thisinvention comprise nonionic surfactants such as polyoxyalkylene polyolsand esters thereof, and anionic surfactants such as salts of alkylsulfonic acids. Such anti-rust compounds are known and can be made byconventional means. Nonionic surfactants, useful as anti-rust additivesin the oleaginous compositions of this invention, usually owe theirsurfactant properties to a number of weak stabilizing groups such asether linkages. Nonionic anti-rust agents containing ether linkages canbe made by alkoxylating organic substrates containing active hydrogenswith an excess of the lower alkylene oxides (such as ethylene andpropylene oxides) until the desired number of alkoxy groups have beenplaced in the molecule.

The preferred rust inhibitors are polyoxyalkylene polyols andderivatives thereof. This class of materials are commercially availablefrom various sources: Pluronic Polyols from Wyandotte ChemicalsCorporation; Polyglycol 112-2, a liquid triol derived from ethyleneoxide and propylene oxide available from Dow Chemical Co.; and Tergitol,dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon,polyalkylene glycols and derivatives, both available from Union CarbideCorp. These are but a few of the commercial products suitable as rustinhibitors in the improved composition of the present invention.

In addition to the polyols per se, the esters thereof obtained byreacting the polyols with various carboxylic acids are also suitable.Acids useful in preparing these esters are lauric acid, stearic acid,succinic acid, and alkyl- or alkenyl-substituted succinic acids whereinthe alkyl- or alkenyl group contains up to about twenty carbon atoms.

The preferred polyols are prepared as block polymers. Thus, ahydroxy-substituted compound, R-(OH)n (wherein n is 1 to 6, and R is theresidue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) isreacted with propylene oxide to form a hydrophobic base. This base isthen reacted with ethylene oxide to provide a hydrophylic portionresulting in a molecule having both hydrophobic and hydrophylicportions. The relative sizes of these portions can be adjusted byregulating the ratio of reactants, time of reaction, etc., as is obviousto those skilled in the art. Thus it is within the skill of the art toprepare polyols whose molecules are characterized by hydrophobic andhydrophylic moieties which are present in a ratio rendering rustinhibitors suitable for use in any lubricant composition regardless ofdifferences in the base oils and the presence of other additives.

If more oil-solubility is needed in a given lubricating composition, thehydrophobic portion can be increased and/or the hydrophylic portiondecreased. If greater oil-in-water emulsion breaking ability isrequired, the hydrophylic and/or hydrophobic portions can be adjusted toaccomplish this.

Compounds illustrative of R-(OH)n include alkylene polyols such as thealkylene glycols, alkylene triols, alkylene tetrols, etc., such asethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol,mannitol, and the like. Aromatic hydroxy compounds such as alkylatedmono- and polyhydric phenols and naphthols can also be used, e.g.,heptylphenol, dodecylphenol, etc.

Other suitable demulsifiers include the esters disclosed in U.S. Pat.Nos. 3,098,827 and 2,674,619.

The liquid polyols available from Wyandotte Chemical Co. under the namePluronic Polyols and other similar polyols are particularly well suitedas rust inhibitors. These Pluronic Polyols correspond to the formula:##STR25## wherein x,y, and z are integers greater than 1 such that the--CH₂ CH₂ O-- groups comprise from about 10% to about 40% by weight ofthe total molecular weight of the glycol, the average molecule weight ofsaid glycol being from about 1000 to about 5000. These products areprepared by first condensing propylene oxide with propylene glycol toproduce the hydrophobic base ##STR26## This condensation product is thentreated with ethylene oxide to add hydrophylic portions to both ends ofthe molecule. For best results, the ethylene oxide units should comprisefrom about 10 to about 40% by weight of the molecule. Those productswherein the molecular weight of the polyol is from about 2500 to 4500and the ethylene oxide units comprise from about 10% to about 15% byweight of the molecule are particularly suitable. The polyols having amolecular weight of about 4000 with about 10% attributable to (CH₂ CH₂O) units are particularly good. Also useful are alkoxylated fattyamines, amides, alcohols and the like, including such alkoxylated fattyacid derivatives treated with C₉ to C₁₆ alkyl-substituted phenols (suchas the mono- and di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl andtridecyl phenols), as described in U.S. Pat. No. 3,849,501, which isalso hereby incorporated by reference in its entirety.

These compositions of our invention may also contain other additivessuch as those previously described, and other metal containingadditives, for example, those containing barium and sodium.

The lubricating composition of the present invention may also includecopper lead bearing corrosion inhibitors. Typically such compounds arethe thiadiazole polysulphides containing from 5 to 50 carbon atoms,their derivatives and polymers thereof. Preferred materials are thederivatives of 1,3,4-thiadiazoles such as those described in U.S. Pat.Nos. 2,719,125; 2,719,126; and 3,087,932; especially preferred is thecompound 2,5 bis (t-octadithio)-1,3,4-thiadiazole commercially availableas Amoco 150. Other similar materials also suitable are described inU.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043;4,188,299; and 4,193,882.

Other suitable additives are the thio and polythio sulphenamides ofthiadiazoles such as those described in U.K. Pat. Specification1,560,830. When these compounds are included in the lubricatingcomposition, we prefer that they be present in an amount from 0.01 to10, preferably 0.1 to 5.0 weight percent based on the weight of thecomposition.

Some of these numerous additives can provide a multiplicity of effects,e.g. a dispersant-oxidation inhibitor. This approach is well known andneed not be further elaborated herein.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts effective to provide their normalattendant function. Representative effective amounts of such additives(as the respective active ingredients) in the fully formulated oil areillustrated as follows:

    ______________________________________                                                         Wt. % A.I.                                                                              Wt. % A.I.                                         Compositions     (Preferred)                                                                             (Broad)                                            ______________________________________                                        Viscosity Modifier                                                                             0.01-4    0.01-12                                            Detergents       0.01-3    0.01-20                                            Corrosion Inhibitor                                                                            0.01-1.5  .01-5                                              Oxidation Inhibitor                                                                            0.01-1.5  .01-5                                              Dispersant       0.1-8      .1-20                                             Pour Point Depressant                                                                          0.01-1.5  .01-5                                              Anti-Foaming Agents                                                                            0.001-0.15                                                                              .001-3                                             Anti-Wear Agents 0.001-1.5 .001-5                                             Friction Modifiers                                                                             0.01-1.5  .01-5                                              Mineral Oil Base Balance   Balance                                            ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the novel dispersants of this invention (inconcentrate amounts hereinabove described), together with one or more ofsaid other additives (said concentrate when constituting an additivemixture being referred to herein as an additive-package) whereby severaladditives can be added simultaneously to the base oil to form thelubricating oil composition. Dissolution of the additive concentrateinto the lubricating oil may be facilitated by solvents and by mixingaccompanied with mild heating, but this is not essential. Theconcentrate or additive-package will typically be formulated to containthe additives in proper amounts to provide the desired concentration inthe final formulation when the additive-package is combined with apredetermined amount of base lubricant. Thus, the dispersants of thepresent invention can be added to small amounts of base oil or othercompatible solvents along with other desirable additives to formadditive-packages containing active ingredients in collective amounts oftypically from about 2.5 to about 90%, and preferably from about 15 toabout 75%, and most preferably from about 25 to about 60% by weightadditives in the appropriate proportions with the remainder being baseoil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (A.I.) content of theadditive, and/or upon the total weight of any additive-package, orformulation which will be the sum of the A.I. weight of each additiveplus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight, unless otherwise notedand which include preferred embodiments of the invention. In theExamples, wt.% ethylene in the polymers is determined by FTIR (ASTMMethod D3900). In the Examples, the "reference oil" is as defined abovefor Formula IV.

EXAMPLE 1 Preparation of Ethylene-Propylene Copolymer

A stirred 1500 cc steel autoclave reaction vessel which is equipped toperform continuous Ziegler polymerization reactions at pressures up to2500 bar and temperatures up to 300° C. is used. The reaction system issupplied with a thermocouple and pressure transducer to measuretemperature and pressure continuously, and with means to supplycontinuously purified compressed ethylene and 1-propene. Equipment forcontinuously introducing a measured flow of catalyst solution at highpressure and equipment for rapidly venting and quenching the reactionand for collecting the polymer product used in the reaction system. Inthis example, the polymerization is performed with a molar ratio of1-propene to ethylene in the feed of 6.0 without the addition of asolvent. 1-Propene and ethylene at this molar ratio are continuouslypumped into the reactor at a mass flow rate of 40 kg/hour and at areactor pressure of 1300 bar. The reactor contents are stirredcontinuously at a rate of 1500 rpm. The temperature of the reactor ismaintained at 175° C. by pumping in a catalyst solution using acontinuous high pressure injection pump at a rate of 1.7 liters/hour.The catalyst solution is prepared by mixing 2.035 grams of racemicdimethylsilyl bridged 3,3'-bis(methylcyclopentadienyl) zirconiumdichloride with 2.0 liters of 10 wt.% (1.4 molar in Al) methylalumoxane(Ethyl Corporation) and 8 liters o f toluene. The yield of liquidethylene-propene copolymer product is 3 kg/hour. The copolymer producthas a number average molecular weight of 670 and a composition of 43mole % propene. The copolymer product is analyzed by FTIR and about 84%of the polymer chains are found to have terminal ethenylideneunsaturation.

EXAMPLE 2 Preparation of Ethylene-Propylene Copolymer

The ethylene-propene copolymer in this Example is prepared using thesame equipment and procedure as in Example 1 with the exception that thetemperature in the reactor is maintained at 175° C. by continuouslypumping in 1.8 liters/hour of a catalyst solution prepared by mixing 198g. of bis(cyclopentadienyl) zirconium dichloride with 1.0 liter of 10wt.% (1.4 molar in Al) methylalumoxane (Ethyl Corporation) and 8 litersof toluene. The yield of liquid ethylene-propene copolymer product is2.9 kg/hour. The copolymer product has a number average molecular weightof 895 and a composition of 44 mole % propene. The copolymer product isanalyzed by FTIR and 95% of the polymer chains are found to haveterminal ethenylidene unsaturation.

EXAMPLE 3 Preparation of Ethylene-Propylene Copolymer

The ethylene-propene copolymer in this Example is prepared using thesame equipment, procedure and catalyst solution as in Example 1 with theexception that the temperature in the reactor is maintained at 200° C.by continuously pumping in 0.54 liters/hour. The yield of liquidethylene-propene copolymer product is 4.7 kg/hour. The copolymer producthas a number average molecular weight of 1040 and a composition of 40mole % propene. The copolymer product is analyzed by FTIR and 84% of thepolymer chains are found to have terminal ethenylidene unsaturation.

EXAMPLES 4-6 Halogenation

In a series of runs, the selected moles of the selected liquid EPcopolymers are charged under dry N₂ at atmospheric pressure to a 500 ml.reactor equipped with a stirrer and a thermocouple and heated by meansof an electric heating mantle. No added solvent or diluent for thereactants is employed. In each run, the reaction mixture is heated to60° C. and C₁₂ is bubbled through the liquid polymer at 60° C. for theselected time while stirring. Dry gaseous nitrogen is passed through theliquid to purge unreacted Cl₂ and HCl. The liquid product containing thechlorinated EP and unreacted EP is analyzed for chlorine.

The data thereby obtained are summarized in Table I.

                  TABLE I                                                         ______________________________________                                        Feed                                                                                            Copolymer As                                                Ex-               Prepared In Cl.sub.2 Time                                                                        Cl-EP                                    ample EP Copolymer                                                                              Example     (Hrs.) (Wt. % Cl)                               ______________________________________                                        4     -- M.sub.n = 670                                                                          1           3      5.07                                     5     -- M.sub.n = 840                                                                          2           3.4    3.89                                     6      -- M.sub.n = 1040                                                                        3           4.7    3.16                                     ______________________________________                                         NOTES:                                                                        EP  ethylenepropylene copolymer.                                         

EXAMPLES 7-9 Preparation of Polyamine Dispersants

A series of dispersant materials are prepared employing 250 g. of theCl-EP products prepared as in Examples 4 to 6.

The Cl-EP polymers are dissolved in 250 cc toluene and charged under N₂blanket to a 1 liter round-bottom reaction flask provided with stirrer,thermometer and chilled H₂ O condenser. To the polymer solution is addedethylene diamine and the mixture is heated to 140° C. under N₂ whilestirring for 3 to 4 hours. The selected amount of calcium oxide is thenadded with stirring to neutralize the HCl by-product, and is thenfiltered. In Examples 8 and 9, an additional 250 ml. of toluene is addedwith stirring for 0.5 hour to dilute the product for ease of filtration.

The resulting product is filtered and analyzed. The data therebyobtained are summarized in Table II below.

                  TABLE II                                                        ______________________________________                                                     Dispersant Analysis                                                      EDA     CaO                   Non-volatile                            Example #                                                                             (g)     (g)    Wt. % N                                                                              Wt. % Cl                                                                              Matter                                  ______________________________________                                        7       210.4   39.3   1.21   1.27    50.2 wt. %                              8       164.1   30.6   0.58   0.67    37.2 wt. %                              9       145.4   27.1   0.47   0.66    38.6 wt. %                              ______________________________________                                         Notes:                                                                        EDA = ethylene diamine.                                                  

EXAMPLE 10 Reduction of Intake Valve Deposits

Two 100 hour test runs are made on a standard mileage accumulationdynometer using a 1987 BMW 325 automobile. In Test 1, an unleadedpremium gasoline (93 RON) without any additives is tested. In Test 2, ablend of the same gasoline and 800 ppm by weight of the dispersantproduct of Example 7 is tested. In Test 3, a blend of the same gasolineand 800 ppm by weight of the dispersant product of Example 9 is tested.Following each test, the intake valves are weighed and the weightobtained compared to the weight of the valves before the test. Thedifference is the total valve deposit weight. The results obtained isshown in Table III below.

                  TABLE III                                                       ______________________________________                                                               Average Deposit                                        Test No.    Diamine, ppm                                                                             Weight, mg/valve                                       ______________________________________                                        1           --         235                                                    2           800        171                                                    3           800         71                                                    ______________________________________                                    

The data in Table III show that intake valve deposits are significantlyreduced when the fuel contains the dispersant materials of thisinvention.

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art withoutdeparting from the spirit of the invention.

What is claimed is:
 1. An additive useful in oleaginous compositionswhich comprises an ethylene alpha-olefin polymer substituted with atleast one amine compound, wherein said amine compound is directlyattached to the backbone of the polymer, wherein said polymer comprisesmonomer units derived from ethylene and at least one alpha-olefin of theformula H₂ C═CHT¹ wherein T¹ is an alkyl group of from 1 to 18 carbonatoms, wherein said polymer has a number average molecular weight offrom about 300 to 20,000 and an average of at least about 30% of saidpolymer chains contain terminal ethenylidene unsaturation prior to beingsubstituted with said amine compound, and wherein said additive ischaracterized by a VR value of less than about 4.1.
 2. The additive ofclaim 1 wherein said polymer has a number average molecular weight ofbetween about 700 and about 20,000.
 3. The additive of claim 2 whereinsaid number average molecular weight is between about 1500 and 10,000.4. The additive of claim 1 wherein said polymer has a molar ethylenecontent of between about 20 and about 80 percent.
 5. The additive ofclaim 1 wherein said polymer has a molar ethylene content of betweenabout 45 and about 65 percent.
 6. The additive of claim 5 wherein saidVR value is less than 4.0.
 7. The additive of any of claims 1 to 6wherein said polymer comprises an ethylene-propylene copolymer.
 8. Anadditive useful in oleaginous compositions which comprises an ethylenealpha-olefin polymer substituted with at least one amine, said polymercomprising monomer units derived from ethylene and at least onealpha-olefin of the formula H₂ C═CHT¹ wherein T¹ is an alkyl group offrom 1 to 2 carbon atoms, and wherein said polymer has a number averagemolecular weight of from about 700 to 20,000 and an average of at leastabout 60% of said polymer chains contain terminal ethenylideneunsaturation and wherein said additive is characterized by a VR value ofless than about 4.1.
 9. The additive of claim 8 wherein said polymercontains from about 3 to 70 mole % ethylene.
 10. The additive of claim 9wherein said polymer contains from about 45 to 6 mole % ethylene. 11.The additive of claim 9 wherein said polymer comprises aethylene-propylene copolymer.
 12. The additive of claim 11 wherein saidpolymer has a number average molecular weight of from about 900 andabout 15,000.
 13. The additive of claim 12 wherein said polymer has anumber average molecular weight of from about 900 and about 15,000. 14.An oil soluble dispersant mixture useful as a fuel or lubricating oiladditive comprising an adduct of:(a) an ethylene alpha-olefin polymersubstituted with halide moieties, said polymer comprising monomer unitsderived from ethylene and at least one alpha-olefin of the formula H₂C═CHT¹ wherein T¹ is an alkyl group of from 1 to 18 carbon atoms, andwherein said polymer has a number average molecular weight of from about300 to 10,000 and an average of at least about 30% of said polymerchains contain terminal ethenylidene unsaturation and wherein saidadditive is characterized by a VR value of less than about 4.1, and (b)at least one amine, said dispersant having a VR' value of less thanabout 4.1.
 15. The dispersant adduct according to claim 14 wherein thelubricating oil dispersant is characterized by a VR'/VR_(r) value ratioof less than about 1.11.
 16. The dispersant adduct according to claim 14wherein the amine contains from 2 to 60 carbon atoms and from 1 to 12nitrogen atoms per molecule.
 17. The dispersant adduct according toclaim 16 wherein said amine comprises a polyalkylenepolyamine whereinsaid alkylene group contains 2 to 60 carbons and saidpolyalkylenepolyamine contains from 2 to about 9 nitrogen atoms permolecule.
 18. The dispersant adduct according to claim 17 wherein saidamine comprises polyethylenepolyamine.
 19. The dispersant adduct of anyone of claims 14 to 18 wherein said alpha-olefin is propylene.
 20. Alubricating oil concentrate containing from about 20 to 60 wt. % of thedispersant of claim
 14. 21. A lubricating oil composition containingfrom about 0.1 to 20 wt. % of the dispersant of claim
 14. 22. Alubricating oil concentrate containing from about 1 to 80 wt. % of thesubstituted ethylene alpha-olefin polymer of claim
 1. 23. A lubricatingoil composition containing from about 5 to 70 wt. % of the substitutedethylene alpha-olefin polymer of claim 1.